Tear resistant gels and articles for every uses

ABSTRACT

Soft, tear resistant gel, gel composites and gel articles for various uses formed from one or a mixture of two or more block copolymers with or without one or more selected other polymers and additives in combination with one or more selected plasticizers being in sufficient amounts to achieve a gel rigidity of from about 20 gram Bloom to about 1,800 gram Bloom.

RELATED APPLICATIONS

This application is a continuation-in-part (C-I-P) of the followingapplications: Ser. No. 08/288,690 filed Aug. 11, 1994 (now U.S. Pat. No.5,633,286); Ser. No. 08/581,125 filed Dec. 29, 1995 (now U.S. Pat. No.5,962,572) are C-I-P of the following applications: Ser. No. 08/665,343,filed Jun. 17, 1996; Ser. No. 09/517,230, filed Mar. 2, 2000 nowabandoned; Ser. No. 09/721,213, filed Nov. 21, 2000 now U.S. Pat. No.6,687,253; Ser. No. 09/896,047, filed Jun. 30, 2001; Ser. No.10/199,361, filed Jul. 20, 2002 now U.S. Pat. No. 7,134,236; Ser. No.10/199,364, filed Jul. 20, 2002 now U.S. Pat. No. 6,794,440; Ser. No.10/199,362, filed Jul. 20, 2002 now U.S. Pat. No. 7,108,873; Ser. No.10/199,363, filed Jul. 20, 2002 now U.S. Pat. No. 7,108,873; Ser. No.10/273,828, filed Oct. 17, 2002 now U.S. Pat. No. 6,909,220; Ser. No.10/299,073, filed Nov. 18, 2002 now abandoned; Ser. No. 10/334,542,filed Dec. 31, 2002 now U.S. Pat. No. 7,159,259; Ser. No. 10/420,487,filed Apr. 21, 2003; Ser. No. 10/420,488, filed Apr. 21, 2003 now U.S.Pat. No. 7,134,929; Ser. No. 10/420,489, filed Apr. 21, 2003; Ser. No.10/420,490, filed Apr. 21, 2003 now U.S. Pat. No. 7,105,607; Ser. No.10/420,491, filed Apr. 21, 2003 now U.S. Pat. No. 7,093,599; Ser. No.10/420,492, filed Apr. 21, 2003; Ser. No. 10/420,493, filed Apr. 21,2003 now U.S. Pat. No. 7,067,583; Ser. No. 10/613,567, filed Jul. 2,2003 now U.S. Pat. No. 7,093,316; Ser. No. 10/675,509, filed Sep. 30,2003; Ser. No. 10/746,196, filed Dec. 25, 2003; in turn U.S. Ser. Nos.:10/746,196, 10/613,567, 10/420,493, 10/420,492, 10/420,488, 10/420,487,10/420,489, 10/420,490, 10/420,492, 10/420,487, 10/334,542, and10/299,073 are C-I-P of U.S. Ser. No.: 08/130,545 filed Oct. 1, 1993,now U.S. Pat. No. 5,467,626, Ser. Nos. 08/288,690, 08/581,125,08/581,188, 08/581,191 filed Dec. 29, 1995, now U.S. Pat. No. 5,760,117,Ser. Nos. 08/612,586, 08/665,343, 08/719,817, 08/863,794, 08/909,487filed Aug. 12, 1997, now U.S. Pat. No. 6,050,871, Ser. Nos. 08/954,424filed Oct. 20, 1997, now U.S. Pat. No. 6,333,374, Ser. No. 08/984,459filed Dec. 3, 1997, now U.S. Pat. No. 6,324,703, Ser. No. 09/230,940filed Feb. 3, 1999, now U.S. Pat. No. 6,161,555, Ser. Nos. 09/274,498,09/285,809, 09/412,886 filed Oct. 5, 1999, now abandoned;PCT/US97/17534, filed 30 Sep. 1997; in turn U.S. Ser. No.: 09/721,213 isa Ser. No. 08/665,343; in turn U.S. Ser. Nos.: 09/412,887, 10/273,828,09/412,886, and 09/412,887 are C-I-P of U.S. Ser. Nos.: 08/130,545,08/665,343, 08/719,817 filed Sep. 30, 1996, now U.S. Pat. No. 6,148,830,Ser. No. 08/863,794 filed May 27, 1997, Ser. Nos. 08/909,487,08/984,459, 09/274,498 filed Mar. 28, 1999, now U.S. Pat. No. 6,420,475,Ser. No. 09/285,809 filed Apr. 1, 1999, now abandoned, Ser. Nos.08/288,690, 08/581,125, 08/581,188, 08/581,191; in turn U.S. Ser. Nos.:10/199,363, 10/199,362, 10/199,361, 09/412,887 filed Oct. 6, 1997, nowabandoned, Ser. No. 10/273,828 are c-i-p of 08/612,586 filed Apr. 8,1996, now U.S. Pat. No. 6,552,109, and 08/288,690; in turn U.S. Ser.Nos.: 08/581,125, 08/581,188 filed Dec. 29, 1995, now abandoned, andSer. No. 08/581,191 are C-I-P of U.S. Ser. No.: 08/288,690;PCT/US94/07314, filed Jun. 27, 1994; PCT/US94/04278, filed 19 Apr. 1994.The subject matter contained in the related applications and patents arespecifically incorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to gels, gel composites and gel articles.

DESCRIPTION OF THE DRAWINGS

FIGS. 1, 2 a-2 d, 3 a-3 n, and 4 a-4 w are representative composites ofthe invention gels.

FIGS. 5 a-5 m are representative of floss designs of the invention gels.

SUMMARY OF THE INVENTION

The invention comprises gels which can be formed into any desired shapefor various uses including adherent gels, adherent gel articles,non-adherent gels, non-adherent gel articles, composite blend gels,composite blend gel articles, gel composites, and gel compositearticles. The invention gels can be formed from one or more polymers.The composite blend gels can be formed from: two or more polymers, twoor more polymers with a selected material, one or more selected polymerswith one or more selected materials, one or more polymers with aselected material, a selected polymer with a selected material, and aselected polymer with one or more selected materials.

The selected polymers useful in forming the invention gels include blockcopolymers, random copolymers, control distribution copolymers, linearcopolymers, radial copolymers, interpolymers, homopolymers. The selectedmaterials are selected from the group consisting of paper, foam,plastic, fabric, metal, foil, concrete, wood, glass, various natural andsynthetic fibers, glass fibers, ceramics, synthetic resin, refractorymaterials, and the like.

The invention gels, gel articles, composite gel blends, gel composites,and gel composite articles can be made to include (a.) internallyblended polymers and materials and (b.) externally applied polymers andmaterials of any desired configuration, finish fineness, thinness,coarseness, roughness, form, shape, and size. Configuration of thepolymers and materials which are useful in the invention include films,sheets, rods, webs, tubes, strands, tapes, aggregates, pellets,platelets, powders, flakes, and the like.

As used herein, the term “gel rigidity” in gram Bloom is determined bythe gram weight required to depress a gel a distance of 4 mm with apiston having a cross-sectional area of 1 square centimeter at 23° C.

The various aspects and advantages of the invention will become apparentto those skilled in the art upon consideration of the accompanyingdisclosure.

DESCRIPTION OF THE INVENTION

A internet search of the USPTO Patent Data Base of Applicant's publishedpatent applications and issued patents describe gel compositions usefulfor fishing identified: U.S. Pat. Nos. 6,627,275, 6,552,109, 6,420,475,6,161,555, 6,333,374, 6,324,703, 6,148,830, 6,117,176, 6,050,871,6,033,283, 5,962,572, 5,938,499, 5,884,639, 5,868,597, 5,760,117,5,655,947, 5,633,286, 5,624,294, 5,475,890, 5,336,708, 5,324,222,5,239,723, 5,508,334, 5,334,646, 5,2624,68, 5,153,254, PCT/US97/17534,PCT/US94/04278 and PCT/US94/07314 which are incorporated herein byreference.

FIGS. 1-39 representative of fishing bait shapes in my copendingapplication Ser. No. 10/199,364; FIGS. 1-23 of copending applicationSer. No. 10/675,509; FIGS. 1a-15n of copending application Ser. No.10/613,567; and FIGS. 1a-11 of U.S. Pat. No. 6,050,871, and FIGS. 1-3 ofU.S. Pat. No. 5,633,286 are incorporated herein by reference. Patentdocuments cited in my application Ser. Nos. 10/746,196, 10/613,567, and10/675,509 are incorporated herein by reference.

Block and other copolymers are described in the following publications:(1) W. P. Gergen, “Uniqueness of Hydrogenated Block Copolymers forFlastomeric Applications,” presented at the German Rubber Meeting,Wiesbaden, 1983; Kautsch, Gummi, Kunstst. 37, 284 (1984). (2) W. P.Gergen, et al., “Hydrogenated Block Copolymers,” Paper No. 57, presentedat a meeting of the Rubber Division ACS, Los Angeles, Apr. 25, 1985.Encyclopedia of Polymer Science and Engineering. Vol. 2, pp 324-434,“Block Copolymers”. (3) L Zotteri and et al., “Effect of hydrogenationon the elastic properties of poly(styrene-b-diene-b-styrene)copolymers”, Polymer, 1978, Vol. 19, April. (4) J. Kenneth Craver, etal., Applied Polymer Science, Ch. 29, “Chemistry and Technology of BlockPolymers”, pp. 394429, 1975. (5) Y. Mahajer and et al., “The influenceof Molecular Geometry on the Mechanical Properties of homopolymers andBlock Polymers of Hydrogenated Butadiene and Isoprene” reported underU.S. ARO Grant No. DAAG29-78-G-0201. (6) J. E McGrath, et al., “Linearand Star Branched Butadiene-Isoprene Block Copolymers and TheirHydrogenated Derivatives”, Chem. Dept, Virginia Polytechnic Instituteand State University Blacksturg, Va., reported work supported by ArmyResearch Office. (7) Legge, Norman R., “Thermoplastic Elastomers”,Charles Goodyear Medal address given at the 131st Meeting of the RubberDivision, American Chemical Society, Montreal, Quebec, Canada, Vol. 60,G79-G115, May 26-29, 1987. (8) Falk, John Carl, and et al., “Synthesisand Properties of Ethylene-Butylene-1 Block Copolymers”, Macromolecules,Vol. 4, No. 2, pp. 152-154, March-April 1971. (9) Morton, Maurice, andet al., “Elastomeric Polydiene ABA Triblock Copolymers withinCrystalline End Blocks”, University of Arkon, work supported by GrantNo. DMR78-09024 from the National Science Foundation and ShellDevelopment Co. (10) Yee, A. F., and et al., “Modification of PS byS-EB-S Block Copolymers: Effect of Block Length”, General ElectricCorporate Research & Development, Schenectady, N.Y. 12301. (11)Siegfried, D. L., and et al., “Thermoplastic Interpenetrating PolymerNetworks of a Triblock Copolymer elastomer and an lonomeric PlasticMechanical Behavior”, Polymer Engineering and Science, January 1981,Vol. 21, No. 1, pp 39-46. (12) Clair, D. J., “S-EB-S Copolymers ExhibitImproved Wax Compatibility”, Adhesives Age, November, 1988. (13) ShellChemical Technical Bulletin SC:1102-89, “Kraton® Thermoplastic Rubbersin oil gels”, April 1989. (14) Chung P. Park and George P. Clingerman,“Compatibilization of Polyethylene-Polystyrene Blends withEthylene-Styrene Random Copolymers”, the Dow Chemical Company, May 1996.(15) Steve Hoenig, Bob Turley and Bill Van Volkenburgh, “MaterialProperties and Applications of Ethylene-Styrene Interpolymers”, the DowChemical Company, September 1996. (16) Y. Wilson Cheung and Martin J.Guest, “Structure, Thermal Transitions and Mechanical Properties ofEthylene/Styrene Copolymers”, the Dow Chemical Company, May 1996. (17)Teresa Plumley Kajaia, Y. Wilson Cheung and Martin J. Guest, “MeltRheology and Processability of Ethylene/Styrene Interpolymers”, the DowChemical Company, May 1997. (18) D.C. Prevorsek, et al., “Origins ofDamage Tolerance in Ultrastrong Polyethylene Fibers and Composites:Journal of Polymer Science: Polymer Symposia No. 75, 81-104 (1993). (19)Chen, H., et al, “Classification of Ethylene-Styrene Interpolymers Basedon Comonomer Content”, J. Appl. Polym. Sci., 1998, 70, 109. (20-24) U.S.Pat. Nos. 5,872,201; 5,460,818; 5,244,996; EP 415815A; JPO7,278,230.(25) Alizadeh, et at., “Effect of Topological Constraints on TheCrystallization Behavior of Ethylene/alp[ha-Olefin Copolymers”, PMSE,Vol, 81, pp. 248-249, Aug. 22-26, 1999. (26) Guest, et al.,“Structure/Property Relationships of Semi-Crystalline Ethylene-StyreneInterpolymers (ESI)”, PMSE, Vol, 81, pp. 371-372, Aug. 22-26, 1999. (27)A. Weill and R. Pixa, in Journal of Polymer Science Symposium, 58,381-394 (1977), tided: “Styrene-diene Triblock Copolymers: OrientationConditions and Mechanical Properties of the Oriented Materials”. (28)Elastomeric Thermoplastic, Vol. 5, pages 416-430; Block Copolymers, Vol.2, pages 324; Block and Graft Copolymers; Styrene-Diene BlockCopolymers, Vol. 15, pages 508-530; and Microphase Structure, can befound in ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, 1987. (29)Legge, N. R, et al., Chemistry and Technology of Block Polymers, Ch. 29,pages 394-429, ACS, Organic Coatings and Plastics Chemistry, ©1975. (30)Legge, N. R., Thermoplastic Elastomers, Rubber Chemistry and Technology,Vol. 60, pages G79-117. (31) Lindsay, G. A., et al., Morphology of LowDensity Polyethylene/EPDM Blends Having Tensile Strength Synergism,source: unknown. (32) Cowie, J. M. G., et al., Effect of Casting on theStress-Hardening and Stress-Softening Characteristics of Kraton-G 1650Copolymer Films, J. Macromol. Sci. Phys., B16(4), 611-632 (1979). (33)Futamura, S., et al., Effects of Center Block Structure on the Physicaland Rheological Properties of ABA Block Copolymers. Part 11. RheologicalProperties, Polymer Engineering and Science, August, 1977, Vol. 17, No.8, pages 563-569. (34) Kuraray Co., LTD. MSDS, Kuraray Septon 4055,Hydrogenated Styrene Isoprene/Butadiene Block Copolymer, Apr. 25, 1991.(35) Hoening, et al. U.S. Pat. No.: 6,156,842, May 23, 2000, “Structuresand fabricated articles having shape memory made from.Alpha-olefin/vinyl or vinylidene aromatic and/or hindered aliphaticvinyl or vinylidene interpolymers. (36) Shell Technical bulletin SC:1102-89 “Kraton® Thermoplastic Rubbers in oil gels”, April 1989. (37)Witco products literature #19610M 700-360“White oils Petrolatum,Microcrystalline Waxes, Petroleum Distillates”, 1996 Witco Corporation.(38) Witco presentation: “White Mineral Oils in ThermoplasticElastomers”, ANTEC 2002, May 5-8, 2002. (39) Lyondell literatureLPC-8126 1/93, “Product Descriptions of White Mineral Oils”, pp 30-33.(40) Collins, Jr., Henry Hill, “COMPLETE FIELD GUIDE TO AMERICANWILDLIFE”, 1959, LCCN: 588880. (41) Romanack, Mark, Bassin' with thePros, 2001, LCCN: 2001086512. (42) Salamone, Joseph C., ConcisePolymeric Materials Encyclopedia, CRC Press, 1999. (43) Lide, David R,Handbook of Chemistry and Physics, CRC Press, 78th Edition, 1997-1998.(44) Sigma year 2002-2003 Biochemical and Reagents for life ScienceResearch, sigma-aldrich.com. (45) Kraton Polymers and Compounds, TypicalProperties Guide, K0137 Brc-00U, 2001. (46) Kraton Thermoplastic Rubber,Typical properties 1988, SC: 68-78, 5/88 5M. (47) Humko chemical ProductGuide, Witco 1988. (48) Opportunities with Humko chemical Kemamide fattyamides, Witco 1987. (49) J. C. Randall, “A Review of High ResolutionLiquid 13 Carbon Nuclear Magnetic Resonance Characterizations ofEthylene-Based Polymers” JMS—Review Macromol. Chem. Phys., C29 (2 & 3),201-317 (1989). (50) US Patent Application publication 20030153681 (Aug.14, 2003) of St Clair, David Jr.; et al. for GELS FROM CONTROLLEDDISTRIBUTION STYRENE BLOCK COPOLYMERS. (51) KRATON® A POLYMERS:EXPANDING STYRENIC BLOCK COPOLYMER TECHNOLOGY by Kathryn J. Wright, etal.: Kraton Polymers US LLC Houston, Tex. (52) RECENT STYRENIC BLOCKCO-POLYMER DEVELOPMENT—DIFFERENTIATED SEPTON AND HYBRAR GRADES byKatsunori Takamoto, et al. (53) US. Patent Application publication2003/0,181,584 of Handlin, Dale Lee Jr.; et al entitled: ELASTOMERICARTICLES PREPARED FROM CONTROLLED DISTRIBUTION BLOCK COPOLYMERS, Sep.25, 2003. (54) Nishikawa, et al., U.S. Pat. No. 5,436,295, Jul. 25,1995. (55) US. Patent Application publication 2003/0,181,585 of Handlin,Dale Lee Jr.; et al entitled: ARTICLES PREPARED FROM HYDROGENATEDCONTROLLED DISTRIBUTION BLOCK COPOLYMERS, Sep. 25, 2003. (56) Paper byKathryn J. Wright, Dale L Handlin, Jr., & Carl L. Willis entitle:“Kraton® A Polymers: Expanding Styrene Block copolymer Technology.

Legge above teaches the development of SEBS triblock copolymers. Clairabove suggests that an S-EB-S polymer retaining at least somecrystallinity in the EB copolymer midblock may be desirable. Therefore,a new family of S-EB-S polymers are developed (U.S. Pat. No. 3,772,234)in which the midblock contains a higher percentage of ethylene. Themolecular weights of the new crystalline midblock segment S-EB-Spolymers can vary from low molecular weight intermediate molecular, tohigh molecular weight; these are designated Shell GR-3, GR-1 and GR-2respectively. Unexpectedly, the highest molecular weight polymer, GR-2exhibits an anomalously low softening poinl A broad melting endotherm isseen in the DSC curves of these polymers. The maximum in this broadendotherm occurs at about 40° C. Himes, et al., (4,880,878) describesSEBS blends with improved resistance to oil absorption.

Papers (14)-(17) describes poly(ethylene-styrene) substantially randomcopolymers (Dow Interpolymers™): Dow S, M and E Series produced bymetallocene catalysts, using single site, constrained geometry additionpolymerization catalysts resulting in poly(ethylene-styrene)substantially random copolymers with weight average molecular weight(Mw) typically in the range of 1×105 to 4×105, and molecular weightdistributions (Mw/Mn) in the range of 2 to 5.

Paper (18) Prevorsek, et al., using Raman spectroscopy, WAXS, SAXD, andEM analysis interprets damage tolerance of ultrastrong PE fibersattributed to the nano scale composite structure that consists ofneedle-like-nearly perfect crystals that are covalently bonded to arubbery matrix with a structure remarkably similar to the structure ofNACRE of abalone shells which explains the damage tolerance and impactresistance of PE fibers. PE because of its unique small repeating unit,chain flexibility, ability to undergo solid state transformation of thecrystalline phase without breaking primary bonds, and its low glasstransition temperature which are responsible for large strain rateeffects plays a key role in the damage tolerance and fatigue resistanceof structures made of PE fibers.

Chen (19) classifies 3 distinct categories of E (approximately 20-50 wt% styrene), M (approximately 50-70 wt % styrene), & S (greater thanapproximately 70 wt % styrene) substantially random or moreappropriately pseudo-random ethylene-styrene copolymers or randomcopolymers of ethylene and ethylene-styrene dyads. The designatedEthylene-styrene copolymers are: E copolymers (ES16, ES24, ES27, ES28,ES28, ES30, and ES44 with styrene wt % of 15.7, 23.7, 27.3, 28.1, 39.6 &43.9 respectively), M copolymers (ES53, E58, ES62, ES63, and ES69 withstyrene wt % of 52.5, 58.1, 62.7, 62.8, and 69.2 respectively andcrystallinity, %, DSC, based on copolymer of 37.5, 26.6, 17.4, 22.9,19.6 and 5.0 respectively), S copolymers (ES72, ES73, and ES74 withstyrene wt % of 72.7, 72.8, and 74.3 respectively). The maximumcomonomer content for crystallization of about 20% is similar in otherethylene copolymers, such as in ethylene-hexene and ethylene-vinylacetate copolymers. If the comonomer can enter the crystal lattice, suchas in ethylene-propylene, compositions in excess of 20 mol % comonomercan exhibit crystallinity. The molecular weight distribution of thesecopolymers is narrow, and the comonomer distribution is homogeneous.These copolymers exhibit high crystalline, lamellar morphologies tofringed micellar morphologies of low crystallinity. Crystallinity isdetermined by DSC measurements using a Rheometric DSC. Specimensweighing between 5 and 10 mg are heated from −80 to 180° C. at a rate of10° C./min (first heating), held at 190° C. for 3 min, cooled to −80° C.at 10° C./min, held at −80° C. for 3 min, and reheated from −80° C. to180° C. at 10° C./min (second heating). The crystallinity (wt %) iscalculated from the second heating using a heat of fusion of 290 J/g forthe polyethylene crystal. Contributing effects of the crystallinityinclude decrease volume fraction of the amorphous phase, restrictedmobility of the amorphous chain segments by the crystalline domains, andhigher styrene content of the amorphous phase due to segregation ofstyrene into the amorphous phase. Table I of this paper shows values ofTotal Styrene (wt % o), a PS (wt %), Styrene (wt % Yo), Styrene (mol %),10-3 Mw, Mw/Mn, and total (wt %) for Ethylene-styrene copolymersES16-ES74 while FIGS. 1-12 of this paper shows: (a) melting thermogramsof ESI 1st and 2nd heating for ES16, ES27, ES44, ES53, ES63, & ES74; (b)crystallinity from DSC as a function of comonomer content; (c)Logarithmic plot of the DSC heat of melting vs. Mole % ethylene forESIs; (d,) measured density as a function of styrene content forsemicrystalline and amorphous ESIs; (e) % crystallinity from density vs% crystallinity from DSC melting enthalpy; (f) Dynamic mechanicalrelaxation behavior; (g) Glass transition temperature as a function ofwt % ethylene-styrene dyads for semicrystalline and amorphous ESIs; (h)Arrhenius plots of the loss tangent peak temperature for representativesemicrystalline and amorphous ESIs; (i) Draw ratio vs engineeringstrain; (j) Engineering stress-strain curves at 3 strain rates for ES27,ES63 and ES74; (k) Engineering stress-strain curves of ESIs; (I)Classification scheme of ESIs based on composition.

(20) U.S. Pat. No. 5,872,201 describes interpolymers: terpolymers ofethylene/styrene/propylene, ethylene/styrene/4 methyl-1-pentene,ethylene/styrene/hexend-1, ethylene/styrene/octene-1, andethylene/styrene/norbornene with number average molecular weight (Mn) offrom 1,000 to 500,000. (21-24) U.S. Pat. Nos. 5,460,818; 5,244,996; EP415815A; JP07,278,230 describes substantially random, more appropriatelypresudo-ramdom copolymers (interpolymers), methods of making and theiruses. (25) Alizadeh, et al., find the styrene interpolymers impedes thecrystallization of shorter ethylene crystallizable sequences and thattwo distinct morphological features (lamellae and fringe micellar orclain clusters) are observed in ethylene/styrene (3.4 mol %) as lamellacrystals organized in stacks coexisting with intertamellar bridge-likestructures. (26) Guest, et al., describes ethylene-styrene copolymershaving less than about 45 wt % copolymer styrene being semicrystalline,as evidenced by a melting endotherm in DSC testing (Dupont DSC-901,10°C./min) data from the second heating curve. Crystallization decreaseswith increasing styrene content. Based on steric hindrance, styrene unitis excluded from the crystalline region of the copolymers. Transitionfrom semicrystalline to amorphous solid-state occurs at about 45 to 50wt % styrene. At low styrene contents (<40%), the copolymers exhibit arelatively well-defined melting process. FIGS. 1-5 of this paper shows(a) DSC data in the T range associated with the melting transition for arange of ESI differing primarily in copolymer styrene content, (b)variation in percent crystallinity (DSC) for ESI as a function ofcopolymer S content, (c) elastic modulus versus T for selected ESIdiffering in S content, (d) loss modulus versus T for selected ESIdiffering in S content, (e) Tensile stress/strain behavior of ESIdiffering in S content, respectively. (27) A. Weill and R. Pixa describetechniques of orientation of neat SIS and SBS block copolymers and theirproperties. (35) Hoening, et al, teaches preparation of interpolymersESI #1 to ESI #38 having number average molecular weight (Mn) greaterthan about 1000, from about 5,000 to about 500,000, more specificallyfrom about 10,000 to about 300,000. (49) J. C. Randall gives acomprehensive review of NMR of ethylene polymers.

(50) US Patent Application publications 2003/0,153,681 filed Feb. 6,2003 and 2004/0,138,371 filed Dec. 22, 2003 describe S-EB-EB/S-EB-Sstyrene block copolymer gels including A-B-A, (A-B)_(n), (A-B)_(n)-A,(A-B-A)_(n)X, (A-B)_(n)X configuration or a mixture thereof, where n isan integer from 2 to about 30, preferably 2 to about 15, more preferably2 to about 6, and X is coupling agent residue. St. Clair furtherdescribes: 100 parts by weight of at least one hydrogenated blockcopolymer having a controlled distribution block of a mono alkenyl areneand conjugated diene and 350 to 2000 parts by weight of an extender oil.The hydrogenated block copolymer has at least one polymer block A and atleast one polymer block B wherein (a) prior to hydrogenation each Ablock is a mono alkenyl arene homopolymer block and each B block is acontrolled distribution copolymer block of at least one conjugated dieneand at least one mono alkenyl arene; (b) subsequent to hydrogenationabout 0-10% of the arene double bonds have been reduced, and at leastabout 90% of the conjugated diene double bonds have been reduced; (c)each A block having a number average molecular weight between about3,000 and about 60,000 and each B block having a number averagemolecular weight between about 30,000 and about 300,000; (d) each Bblock comprises terminal regions adjacent to the A blocks that are richin conjugated diene units and one or more regions not adjacent to the Ablocks that are rich in mono alkenyl arene units; (e) the total amountof mono alkenyl arene in the hydrogenated block copolymer is about 20percent weight to about 80 percent weight; and (f) the weight percent ofmono alkenyl arene in each B block is between about 10 percent and about75 percent. That the key component of his invention is the novel blockcopolymer containing mono alkenyl arene end blocks and a unique midblock of a mono alkenyl arene and a conjugated diene. Surprisingly, thecombination of (1) a unique control for the monomer addition and (2) theuse of diethyl ether or other modifiers as a component of the solvent(which will be referred to as “distribution agents”) results in acertain characteristic distribution of the two monomers (herein termed a“controlled distribution” polymerization, i.e., a polymerizationresulting in a “controlled distribution” structure), and also results inthe presence of certain mono alkenyl arene rich regions and certainconjugated diene rich regions in the polymer block. For purposes hereof,“controlled distribution” is defined as referring to a molecularstructure having the following attributes: (1) terminal regions adjacentto the mono alkenyl arene homopolymer (“A”) blocks that are rich in(i.e., having a greater than average amount of) conjugated diene units;(2) one or more regions not adjacent to the A blocks that are rich in(i.e., having a greater than average number of) mono alkenyl areneunits; and (3) an overall structure having relatively low blockiness.For the purposes hereof, rich in” is defined as greater than the averageamount, preferably greater than 5% of the average amount. Thisrelatively low blockiness can be shown by either the presence of only asingle glass transition temperature (Tg) intermediate between the Tg'sof either monomer alone, when analyzed using differential scanningcalorimetry (“DSC”) thermal methods or via mechanical methods, or asshown via proton nuclear magnetic resonance (“H-NMR”) methods. Thepotential for blockiness can also be inferred from measurement of theUV-visible absorbance in a wavelength range suitable for the detectionof polystyryltithium end groups during the polymerization of the B blockA sharp and substantial increase in this value is indicative of asubstantial increase in polystyryllithium chain ends. In this process,this will only occur if the conjugated diene concentration drops belowthe critical level to maintain controlled distribution polymerization.Any styrene monomer that is present at this point will add in a blockyfashion. The term “styrene blockiness”, as measured by those skilled inthe art using proton NMR, is defined to be the proportion of S units inthe polymer having two S nearest neighbors on the polymer chain. Thestyrene blockiness is determined after using H-1 NMR to measure twoexperimental quantities as follows: First the total number of styreneunits (i.e. arbitrary instrument units which cancel out when ratioed) isdetermined by integrating the total styrene aromatic signal in the H-1NMR spectrum from 7.5 to 6.2 ppm and dividing this quantity by 5 toaccount for the 5 aromatic hydrogens on each styrene aromatic ring.Second, the blocky styrene units are determined by integrating thatportion of the aromatic signal in the H-1 NMR spectrum from the signalminimum between 6.88 and 6.80 to 6.2 ppm and dividing this quantity by 2to account for the 2 ortho hydrogens on each blocky styrene aromaticring. The assignment of this signal to the two ortho hydrogens on therings of those styrene units which have two styrene nearest neighborswas reported in F. A. Bovey, High Resolution NMR of Macromolecules(Academic Press, New York and London, 1972), chapter 6. The styreneblockiness is simply the percentage of blocky styrene to total styreneunits: Blocky %=100 times (Blocky Styrene Units/Total Styrene Units).Expressed thus, Polymer-Bd-S-(S)_(n)-S-Bd-Polymer, where n is greaterthan zero is defined to be blocky styrene. For example, if n equals 8 inthe example above, then the blockiness index would be 80%. It ispreferred that the blockiness index be less than about 40. For somepolymers, having styrene contents of ten weight percent to forty weightpercent, it is preferred that the blockiness index be less than about10. Controlled distribution block copolymers were prepared according tothe process disclosed in copending patent application Ser. No.60/355,210, filed Feb. 7, 2002, entitled Novel Block Copolymers andMethod for Making Same (TH-1768 prov.), and from it's continuingapplication filed concurrently with this application (TH-1768 conv.),Ser. No. 10/359,981, and from U.S. application Ser. No. 10/209,285 filedJul. 31, 2002 (TH-1768×). As is described and incorporated herein forclarity, example 1: controlled distribution block copolymers areprepared according to the process disclosed in copending patentapplication Ser. No. 60/355,210 as referenced, the polymers wereselectively hydrogenated ABA block copolymers where the A blocks werepolystyrene blocks and the B block prior to hydrogenation was a styrenebutadiene controlled distribution block having terminal regions that arerich in butadiene units and a center region that was rich in styreneunits. Step I MW is the molecular weight of the first A block Step II MWis the molecular weight of the AB blocks and Step III MW is themolecular weight of the ABA blocks. The polymers were hydrogenated suchthat greater than about 95% of the diene double bonds have been reduced.

TABLE 1 Controlled Distribution Polymers Styrene 1,2- % Blocki- StyreneB PCS Poly- Step I Step II Step III in Mid ness BD Num- mer MW(k) MW(k)MW(k) Block (%) (%) ber 24 29 159 188 39.7 9 35 58 25 9.1 89 97 25.7 036 39where “MW(k)”=molecular weight in thousands and “PSC(%)”=wt % of styrenein the final polymer. “Styrene Blockiness” is for just the B block.Accordingly, Polymer #24 is a linear ABA tri-block copolymer havingnumber average block mol weights of 29,000-130,000-29,000 and Polymer#25 is a linear ABA tri-block copolymer having number average block molweights of 9,100-80,000-9,100. Example 2 shows the use of the novel CDPolymer #25 in oil gels. Samples #2-1,2-2 and 2-3 show the properties ofgels based on the conventional hydrogenated SBC, SEBS #1. SEBS #1 is aselectively hydrogenated SBS block copolymer having polystyrene endblocks of about 10,000 and a hydrogenated polybutadiene mid block ofabout 50,000. Results show that as the polymer content increases,softening point and tensile properties improve and melt viscosityincreases. Samples #24, 2-5 and 2-6 show that the same trend is foundusing CD Polymer #25. Surprisingly, however, CD Polymer #25 gives thegel higher tensile strength and higher elongation than the conventionalhydrogenated polymer.

TABLE 2 Composition, % w #2-1 #2-2 #2-3 #2-4 #2-5 #2-6 DRAKEOL 34 90 8580 90 85 80 SEBS #1 10 15 20 CD Polymer #25 10 15 20 Melt Vis @ 149° C.,185 750 3,870 235 2210 17,500 cps R&B Softening Pt, 85 96 106 89 104 117° C. Tensile Strength, psi too 17.0 51 too 18.5 79 soft soft Elongation@ Break, 280 540 460 760 %

In example 3, oil gels were made with higher molecular weight polymers,a conventional hydrogenated SEBS #2 and the CD polymer #24. SEBS #2 is aselectively hydrogenated SBS block copolymer having polystyrene endblocks of about 30,000 and a hydrogenated polybutadiene mid block ofabout 130,000. Results show that as the polymer content increases,softening points and melt viscosities increase. The softening points ofsamples #3-3 and 3-4 made using CD Polymer #24 are higher than softeningpoints of samples #3-1 and 3-2 made using SEBS #2. However, meltviscosities of the gels made with CD Polymer #24 are also higher thanthose made with the conventional hydrogenated polymer SEBS #2.

TABLE 3 Composition, % w #3-1 #3-2 #3-3 #3-4 DRAKEOL34 95 92.5 95 92.5SEBS #2 5 7.5 CD Polymer #24 5 7.5 Melt Vis @ 149° C., cps 5950 497002300 133000 Melt Vis @ 177° C., cps 260 1140 905 12300 R&B Softening Pt,° C. 110 124 116 136

The more recent published patent application 2004/0,138,371 also includedescriptions of the present invention gel articles contained in my priorpatent application U.S. Ser. No. 10/675,509 (filed Sep. 30, 2003) ofwhich this and my U.S. Ser. No. 10/746,196 are continuations thereof.(51) Kathryn J. Wright et al., describes S-EB-EB/S-EB-S styrene blockcopolymer RP6935. (52) Katsunori Takamoto, et al., describes styreneblock copolymers Septon 4033, 4044, 4055, 4077, 4099.

(53) Handlin, Dale Lee Jr.; et al., describes representativeS-EB-EB/S-EB-S styrene block copolymers 3, 4, 5, 9 and 11 which are ofthe controlled distribution styrene block copolymer type Kraton GA typehaving improved properties over conventional styrene block copolymertype Kraton G 1651. (54) Nishikawa, et al., describes the reparation ofblock copolymer using a pressure-proof vessel equipped with a stirrerwas charged with 3,000 g of cyclohexane, 50 g of sufficiently dewateredstyrene and 0.01 mole of lithium sec-butyl followed by polymerization at60′. C. for 60 minutes, addition of 200 g of a 50/50 by weight mixtureof isoprene/butadiene followed by polymerization at 60 degree C. for 60minutes and addition of 50 g of styrene followed by polymerization for60 minutes, to obtain a styrene-isoprenell,3-butadiene-styrene blockcopolymer. Hydrogenation was conducted in the same manner as above toobtain a block copolymer having a hydrogenation ratio of 98%. This wasnamed SEEPS-1. The block copolymer's olefinic elastomer block having aglass transition point of not higher than-20 degree C. and a heat offusion of crystal of not more than 8 cal/g. (55) Handlin, Dale Lee Jr.;et al., describes representative S-EB-EB/S-EB-S styrene block copolymers3, 4, 5, 9 and 11 which are of the controlled distribution styrene blockcopolymer type Kraton GA type having improved properties overconventional styrene block copolymer type Kraton G 1651. (56) Kathryn J.Wright, Dale 1 Handlin, Jr., & Carl L. Willis describes representativeS-EB-EBIS-EB-S styrene block copolymers #1, RP6936, and PR6935 with PSC% and Calc. Midblock PSC % 40, 25.7; 40.1, 26; 58, 39.7 respectively.The midblock PSC is calculated from proton NMR analysis. FIG. 1 of thepaper shows the distribution of styrene and butadiene in the midblock ofcontrolled distribution polymer #1. The synthesis technique employedresults in a controlled distribution midblock where the terminal dieneregions adjacent to the styrene endblocks are rich in conjugated dieneunits, the central region of the diene/styrene midblock is rich instyrene, and the overall midblock structure has relatively low styreneblockiness. Adding styrene to the midblock in a controlled distributionincreases the rubber stiffness with only a small increase in the Young'smodulus for RP6936 as compared to a reference. The S-EB-EB/S-EB-S can beformulated with polystyrene (such as PS EA3000) and oils, showscompatibility with PET, PPO and SMMA, Noryl and SAN. The distribution ofstyrene is important to a stiffer stretch response as compared to #2'ssignificantly increased Young's modulus suffering from lower elasticpower and increased plasticity. The other parameter which controlleddistribution of styrene in the midblock provides is a tunable glasstransition temperature (Tg) tunable between −55° C. and 10° C. byvarying the amount of styrene in the midblock. For example PR6935 with aTg of −13° C. can be further adjusted by loading with conventionaladditives to adjust its Tg and broaden the tan delta for dampingapplications. In sum, Kraton A demonstrate improved rubber modulus withslight increase in Young's modulus, when compounded demonstrate improvedflow, isotropy, and elasticity vs concentional SEBS copolymers. Theaddition of styrene to the midblock improves overmolding adhesion tostytene-containing substrates as well as to thermoplastics and COCs.

As part of my disclosure, the patents, patent applications, patentapplication publications, and publication listed, described, andmentioned above and below, including (1) through (58) are incorporatedherein by reference. The gelatinous elastomer compositions of thepresent invention can be made firm, soft, tacky (adherent), non-tacky(non-adherent) to the touch, and made to exhibit no tack. Certainselected additives can be use to achieve non-tacky feel to the inventiongels' surface. In another embodiment, the invention gels' tack can bereduced or completely eliminated without the need of any additivesblooming to the surface for tack reduction or elimination altogether.For simplicity, the gelatinous elastomer compositions of the inventionwhich are highly tear resistant and rupture resistant and can be madetacky, adherent, non-tacky to the touch and optically transparent orclear will be referred to herein as “invention gel(s)” which includes“tear resistant gels”, “rupture resistant gels”, “non-tacky gels”, “notack gels”, “optical gels”, “tacky gels”, “adherent gels”, “crystallinemidblock segment containing gels”, “non-crystalline containing gels”,“low crystalline containing gels”, crystal gels” and the like whenreferring to certain property attributes of the various gels or moresimply refer to as “the gel(s)” or “said gel(s)”. Gels of the inventionare described herein below for every use. In general the copolymers, CDcopolymers, linear, radial copolymers, and multiblock copolymers usefulin forming the invention gels have the general configurations A-B-A,(A-B)_(n), (A-B)_(n)-A, (A-B-A)_(n)X, (A-B)_(n)X, An-B-An, A-B-B/A-B-S,and (An-B)_(n) configuration or a mixture thereof, where n is an integerfrom 2 to about 30, preferably 2 to about 15, more preferably 2 to about6, and X is coupling agent residue; wherein each A_(n) is a selectedglassy polymer end block of a monoalkenyl arene compounds, morespecifically, a monovinyl aromatic compounds such as polystyrene (wheresuperscript n=1), monovinyinaphithalene as well as the alkylatedderivatives thereof such as poly(alpha-methylstyrene) (n=2),poly(o-methylstyrene) (n=3), poly(m-methylstryene) (n=4),poly(p-methylstyrene) (n=5) poly(tertiary-butylstyrene) (n=6), and thelike, and midblocks (B) comprising polymer chains of poly(butylene),poly(ethylene), poly(ethylene) and poly(propylene) or -EEP-, -EB-EB-,-EB-EB/S-EB-, -EB-EB/S-EB-, -EB-EB/S-, -EB-EB-, -EB-EB/S-EB)_(n)-,-EB-EB/S-, -EP-EPIS-EP-, -EB-EP/S-EB-, -EB-EP/S-EP-, and the like.

The invention gel composition comprises at least one high viscositylinear multiblock copolymers, controlled distribution styrenecopolymers, and star-shaped (or radial) copolymers. The invention gelcompositions copolymer comprises 100 parts by weight of one or a mixtureof two or more of a hydrogenated styrene isoprene/butadiene blockcopolymer(s) more specifically, controlled distribution block copolymersand hydrogenated styrene block polymer with 2-methyl-1,3-butadiene and1,3-butadiene) or poly(styrene-ethylene-ethylene-propylene-styrene)SEEPS or poly(styrene-ethylene-ethylene-propylene)_(n), (SEEP)_(n),S-EB-EB/S-EB-S, (S-EB-EB/S-EB)_(n), (S-EB-EB)_(n), (S-EB-EB)_(n)-S,(S-EB-EB/S-EB)_(n)-S, (S-EB-EB/S)_(n).

The controlled distribution (CD) styrene block copolymer type Kraton A(S-B-B/SBS) and hydrogenated version Kraton GA (S-EB-EB/S-EB-S) type CDpolymers are useful in forming the invention gels; they exhibit improvedproperties over conventional styrene block copolymer type Kraton Gincluding improved tear resistant and improved rupture resistant, lowertack, and other improved properties over type Kraton G. Correspondingtype Kraton GA like that of Kraton G1651 exhibit such improvements, suchas CD polymer #25 or RP6936 with a PSC %/o of approximate 40.1 and acalculated midblock PSC %/o of approximately 26. Corresponding typeKraton GA like that of Kraton G1654 exhibit such improvements.Corresponding type Kraton GA of Kraton G1650 exhibit such improvements.Corresponding type Kraton GA of Kraton G1652 exhibit such improvements.While, lower melt viscosity Kraton GA, such as CD polymers #24 or RP6935being more isotropic with a Tg of -13° C. can be compared to G1650 insome respects. In general, all corresponding type Kraton GA like that ofKraton G exhibit such improvements.

The SEEPS, S-EB-EB/S-EB-S, (S-EB-EB/S-EB)_(n), (S-EB-EB)_(n),(S-EB-EB)_(n)—S, (S-EB-EB/S-EB)_(n)—S, and (S-EB-EB/S)_(n) copolymersare characterized as having a Brookfield Viscosity value at 5 weightpercent solids solution in toluene at 30° C. of from less than about 40mPa·s to about 150 mPa·s and higher, advantageously from about 40 mPa·sto about 60 mPa·s and higher, more advantageously from about 50 mPa·s toabout 80 mPa·s and higher, still more advantageously from about 70 mPa·sto about 110 mPa·s and higher, and even more advantageously from about90 mPa·s to about 180 mPa·s and higher than about 350 cps.

In a further embodiment of the invention, ethylene-styrene copolymersare also incorporated to form the invention gels, invention gelcomposites and invention gel articles. These are produced by metallocenecatalysts, using single site, constrained geometry additionpolymerization catalysts resulting in substantially randompoly(ethylene-styrene) copolymers. Representative ethylene-styrenecopolymers are commercially available Dow Interpolymers™, Dow S, M and ESeries (ES16, ES24, ES27, ES28, ES28, ES30, ES44, ES53, ES58, ES62,ES63, ES69, ES72, ES73, ES74 and the like). Such interpolymers can beused in combination with major or minor amounts of SEEPS,S-EB-EB/S-EB-S, (S-EB-EB/S-EB)_(n), (S-EB-EB)_(n), (S-EB-EB)_(n)-S,(S-EB-EB/S-EB)_(n)-S, and (S-EB-EB-S)_(n) copolymers including SEBS,SEPS in forming gels of the invention.

A further embodiment are invention composite gels comprising one or moreselected gel G_(n) with one or more selected material M_(n),characterized by a gel gram Bloom rigidity of about 20 to about 1,800gram bloom, said composite gels are made from 100 parts by weight of oneor more block copolymer with from about 300 to about 1.600 parts byweight of one or more selected plasticizing oils. The amount of one ormore said plasticizing oil(s) can have a viscosity of about 4 cSt at 40°C. and greater with or without one or more of additive; wherein thecopolymer(s), one or more plasticizers, one or more added polymers, andother additive components are combined to form said gelatinouselastomeric composition; wherein said block copolymer comprises theformulas A-B-A, (A-B)_(n), (A-B)_(n)-A, (A-B-A)_(n)X, (A-B), X, An-B-An,(An-B)_(n), A-B-B/A-B-A and the like; said A being selected frommonoalkenylarene polymers including polystyrene; said B being ahydrogenated polymer comprising a plurality of covalently linkedconjugated diene monomers including a hydrogenated polymer ofisoprene/butadiene.

As use herein, the tack level in terms of “Gram Tack” can be determinedby the gram weight displacement force to lift a polystyrene referencesurface by the tip of a 16 mm diameter hemi-spherical gel probe incontact with said reference surface as measured on a scale at 23° C.(about STP conditions). Other methods can be use to measure tack, suchas the well known rolling ball tack, and 90 degree, and 180 degree peelmethods. As used herein, the term “gel rigidity” in gram Bloom isdetermined by the gram weight required to depress a gel a distance of 4mm with a piston having a cross-sectional area of I square centimeter at23° C. As described herein, the conventional term “major” means greaterthan 50 parts by weight and higher (e.g. 5.01, 50.2, 50.3, 50.4, 50.5, .. . 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67,68, 69, . . . 80 and higher, including values in-between based on 100part by weight of copolymers) and the term “minor” means 49.99 parts byweight and lower (e.g. 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38,37, 36, 35, 34, 33, 32, 21, . . . 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9,0.8, 0.7 . . . 0.09, including values in-between and the like) based on100 parts by weight of the base block copolymer(s). When % is use, the %refers to the % of the total of the component(s) parts by weight

The polyethylene crystalline segments midblocks of ethylene-styrenecopolymers, block copolymers, and other polymers forming one or moreembodiments of the invention gels can be characterized by the presenceof a melting trace of from less than about 2.5° C. (for low viscositypolyethylene midblock containing block copolymers) to greater than about18° C. (for higher viscosity polyethylene midblock containing blockcopolymers) as determined by crystallization DSC curve. More specificDSC melting values of the crystalline midblock block segment of theSEEPS, S-EB-EB/S-EB-S, (S-EB-EB/S-EB)_(n), (S-EB-EB)_(n),(S-EB-EB)_(n)—S, (S-EB-EB/S-EB)_(n)—S, and (S-EB-EB/S)_(n) copolymersmay be carefully measured and/or detected include less than about 1.5°C., 2° C., 3° C., 4° C., 5° C., 6° C., 7° C., 8° C., 9° C., 10° C., 11°C., 12° C., 13° C., 14° C., 15° C., 16° C., 17° C., 18° C., 19° C., 20°C., 21° C., 22° C., 23° C., 24° C., 25° C., 26° C., 27° C., 28° C., 29°C., 30° C., 31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37° C., 38°C., 39° C., 40° C., 41° C., 42° C., 43° C., 44° C., 45° C., 46° C., 47°C., 48° C., 49° C., 50° C., 51° C., 52° C., 53° C., 54° C., 55° C., andhigher. Whereas, the melting trace in DSC evidencing the presence ofcrystalline polyethylene are not found in amorphous block copolymerssuch as SEPS.

The crystallization exotherm of the crystalline block copolymerinvention gel are determined by ASTM D 3417 method. In order to provideconditions for DSC samples of certain polyethylene midblock containingblock copolymers to have the best possible chance to exhibit anycrystallinity the measurement protocol can be modified as follows: heatto 140° C. @ 10° C./min., cool to 0° C. @ 2° C./min., put sample infreezer for 1 week, heat sample to 140° C. @ 1° C./min., then cool to 0°C. @1° C./min.

Generally, the method of obtaining long runs of crystalline —(CH₂)—is bysequential block copolymer synthesis followed by hydrogenation. Theattainment of invention gels is solely due to the selectivepolymerization of the butadiene monomer (forming the midblocks)resulting in one or more predetermined amount of 1,4 poly(butadiene)blocks followed by sequential polymerization of additional midblocks andhydrogenation to produce one or more crystalline midblocks of the finalblock copolymers.

The crystalline block copolymers are made by sequential block copolymersynthesis, the percentage of crystallinity or (—CH₂—)16 units can be atleast about (0.67)₄ or about 20% and actual crystallinity of about 12%.For example, a selectively synthesized S-EBn-S copolymer having a ratioof 33:67 of 1,2 and 1,4 poly(butadiene) on hydrogenation will result ina midblock with a crystallinity of (0.67)₄ or 20% o. For sake ofsimplicity, when n is a subscript of -EB-, n denotes the percentage of(—CH₂—)₄ units, eg, n=33 or 20% crystallinity which is the percentage of(0.67)₄ or “(—CH₂—)₁₆” units. Thus, when n=28 or 72% of (—CH₂—)4 units,the % crystallinity is (0.72)₄ or 26.87% crystallinity attributed to(—CH₂—)16 units, denoted by -EB₂₈-. As a matter of convention, and forpurposes of this specification involving hydrogenated polybutadiene: thenotation -E-denotes at least about 85% of (—CH₂—)₄ units. The notation-B-denotes at least about 70% of [—CH₂—CH(CH₂H₅)-] units. The notation-EB-denotes between about 15 and 70% [—CH₂—CH(CH₂H₅] units. The notation-EBn-denotes n % [—CH₂—CH(CH₂H₅)-] units. For hydrogenated polyisoprene:The notation -EP-denotes about at least 90% [—CH₂-CH(CH₃)—CH₂—CH₂—]units.

Generally, one or more (E) midblocks can be incorporated at variouspositions along the midblocks of the block copolymers. The lowerflexibility of block copolymer gels due to (E) midblocks can be balancedby the addition of sequentially (W) midblocks. For example, thesequentially synthesized block copolymer S-E-EB-S can maintain a highdegree of flexibility due to the presence of amorphous -EB-block Thesequential block copolymer S-E-EB-B-S can maintain a high degree offlexibility due to the presence of amorphous -EB- and -B-midblocks. Thesequential block copolymer S-E-EP-E-S can maintain a high degree offlexibility due to the presence of -EP-midblock The sequential blockcopolymer S-E-B-S can maintain a high degree of flexibility due to thepresence of the -B-midblock. For S-E-S where the midblock may becrystalline and flexibility low, physical blending with amorphous blockcopolymers such as S-EP-S, S-EB-EP-S, (S-EP)_(n) and the like canproduce more softer, less rigid, and more flexible gel.

Because of the high viscosity of the block copolymers and (E) midblocks,the invention gel exhibit different physical characteristics andimprovements over amorphous gels including damage tolerance, improvedcrack propagation resistance, improved tear resistance producing knottytears as opposed to smooth tears, improved resistance to fatigue, higherhysteresis, etc. Moreover, the invention gels when stretched exhibitadditional yielding as shown by necking caused by stress inducedcrystallinity or yielding of the styrene glassy phases.

The invention gels can optionally comprise selected major or minoramounts of one or more polymers or copolymers provided the amounts andcombinations are selected without substantially decreasing the desiredproperties. The polymers and copolymers can be linear, star-shaped,branched, or multiarm; these including: (SBS) styrene-butadiene-styreneblock copolymers, (SIS) styrene-isoprene-styrene block copolymers, (lowstyrene content SEBS such as Kraton 1650 and 1652)styrene-ethylene-butylene-styrene block copolymers, (SEP)styrene-ethylene-propylene block copolymers, (SEPS Kraton RP-1618)styrene-ethylene-propylene-styrene block copolymers, (SB)_(n)styrene-butadiene and (SEB)_(n), (SEBS)_(n), (SEP)_(n), (SI)_(n)styrene-isoprene multi-arm, branched or star-shaped copolymers,polyethyleneoxide (EO), poly(dimethylphenylene oxide) and the like.Still, other polymers include homopolymers which can be utilized inminor amounts; these include: polystyrene, polybutylene, polyethylene,polypropylene and the like. In the case of high molecular weight andcombination of high styrene content of the block copolymer which may bethe reason for improve tear and fatigue resistance, these properties maybe achieved and maintained by blending copolymers of SEEPS and CDS-EB-EB/S-EB-S with minor amounts of copolymers of SBS (Kraton D 1101,1144, 1116, 1118, 4141, 4150, 1133, 1184, 4158, 1401P, 4240, and KX219),SEBS (G1651, G1654), SEPS, ES30, ES44, E53, ES58, ES62, ES63, ES69,ES72, ES73, ES74, and the like.

Still other polymers useful in the invention gels include: oftrifluoromethyl-4,5-difuoro-1,3-dioxole and tetrafluoroethylene,polytetrafluoroethylene, maleated poly(styrene-ethylene-butylene),maleated poly(styrene-ethylene-butylene)_(n), maleatedpoly(styrene-ethylene-butylene-styrene), maleatedpoly(styrene-ethylene-propylene)_(n), maleatedpoly(styrene-ethylene-propylene-styrene), poly(dimethylphenylene oxide),poly(ethylene-butylene), poly(ethylene-propylene),poly(ethylene-styrene) interpolymer made by metallocene catalysts, usingsingle site, constrained geometry addition polymerization catalysts,poly(styrene-butadiene), poly(styrene-butadiene)_(n),poly(styrene-butadiene-styrene), poly(styrene-ethylene-butylene),poly(styrene-ethylene-butylene)_(n),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene-propylene-styrene), poly(styrene-isoprene),poly(styrene-isoprene)_(n), poly(styrene-isoprene-styrene),poly(styrene-isoprene-styrene)_(n), polyamide, polybutylene,polybutylene, polycarbonate, polydimethylsiloxane; polyethylene vinylalcohol copolymer, polyethylene, polyethyleneoxide, polypropylene,polystyrene, polyvinyl alcohol, wherein said selected copolymer is alinear, radial, star-shaped, branched or multiarm copolymer, wherein nis greater than one.

When the selected polymers and copolymers contain greater glassy blockof styrene content of 33 and higher or additional low molecular weightpolystyrene is added, such may be effective to provide a Gram Tack lowerthan a invention gels having the same rigidity formed from the blockcopolymers alone with or without one or more first plasticizers incombination with or without one or more second plasticizers. Theselected component polymers of polystyrene forming a styrene content of33 and higher when used in effective amounts can provide a highertemperature compression set than a gelatinous composition having thesame rigidity formed from the block copolymers and corresponding firstplasticizers alone or the first plasticizers with a second plasticizer.The invention gels' self-adhesion also decreases with increasing overall styrene content of the gels. Selection of ESI and SBS with higherstyrene content can provide lower self-adhesion, lower tack, or no tackto the invention gels.

On the other hand, the lower viscosity first plasticizer can impartlower Gram Tack to the invention gels than an increase of styrenecontent of the copolymers or polymers and copolymers. The low tack andnon tacky invention gels can be made from one or more linear, branched,star-shaped (radial), or multiarm block copolymers or mixtures of two ormore such block copolymers having one or more midblock polymer chainswhich invention gels have advantages use as invention gel articles withhigher tear propagation resistance. The invention gels also possess hightensile strength and rapid return from high extension and can exist inan altered state of delay elastomeric recovery as it regains itsoriginal shape following high extensions or dynamic deformations. Theinvention gels also exhibit low heat set, low compression set, low heatdistortion, high dimensional stability, crack, tear, craze, and creepresistance, combination of excellent tensile strength and highelongation, long service life under shear, stress and strain and capableof withstanding repeated dynamic shear, tear and stress forces,excellent processing ability for cast molding, extruding, fiber formingfilm forming and spinning, non-toxic, nearly tasteless and odorless,soft and strong, optically clear, highly flexible, possessing elasticmemory, substantially with little or no plasticizer bleedout, and havinglow or no tack in contact with human hand which reduction in tackinesscan be measured. In one embodiment, the non tacky and optical propertiesof the invention gels need not rely on powders or surface activation byselected additives to establish their non-tackiness. The invention gels'non-tackiness can be pervasive of the gels' entire bulk or volume. Nomatter how deep or in which direction a cut is made, the invention gelscan be made non-tacky throughout (at all points internally as well as onthe gels' surface). Once the gel is cut, the invention gel immediatelyexhibits non-tackiness at its newly cut surface. Hence, the homogeneityof the non-tackiness and optical properties of the invention gels arenot known before the instant invention.

Examples of polymers, block copolymers, copolymers, and blends include:(a) Kraton G 1651, G 1654×; (b) Kraton G 4600; (c) Kraton G 4609; othersuitable high viscosity polymer and oil s include: (d) Tuftec H 1051;(e) Tuftec H 1041; (f) Tuftec H 1052; (g) low viscosity Kuraray SEEPS4033 (hydrogenated styrene isoprene/butadiene block copolymers, morespecifically, hydrogenated styrene block polymer with2-methyl-1,3-butadiene and 1,3-butadiene); (h) Kuraray SEBS 8006; (i)Kuraray SEPS 2005; (j) Kuraray SEPS 2006, and (k) blends (polyblends) of(a)-(h) with other polymers and copolymers include: (1) SEBS-SBS; (2)SEBS-SIS; (3) SEBS-(SEP); (4) SEBS-(SEB)_(n); (5) SEBS-(SEB)_(n); (6)SEBS-(SEP)_(n); (7) SEBS-(SI)_(n); (8) SEBS-(SI) multiarm; (9)SEBS-(SEB)_(n); (10) (SEB)_(n) star-shaped copolymer; (11) s made fromblends of (a)-(k) with other homopolymers include: (12)SEBS/polystyrene; (13) SEBS/polybutylene; (14) SEBS/polyethylene; (14)SEBS/polypropylene; (16) SEP/SEBS, (17) SEP/SEPS, (18) SEP/SEPS/SEB,(19), SEPS/SEBS/SEP, (20), SEB/SEBS (21), EB-EP/SEBS (22), SEBS/EB (23),SEBS/EP (24), (25) (SEB)_(n) s, (26) (SEP)_(n), (27) Kuraray 2007(SEPS), (28) Kuraray 2002, (SEPS).

Other polyblends can include: (29) E-S-E and SEEPS, (30) E-S-E andSEB-EB/S-EB-S, (31) CD SEBS, (32) E-S-E and CD SEBS, (33) SEPS, SEBS andSEEPS, (34) SEEPS and polystyrene, (35) CD SEBS and polystyrene, (36)S-EB-EB/S-EB-S and SEEPS, and the like.

The controlled distribution styrene block copolymers S-EB-EB/S-EB-SKraton GA such as RP6936 and the like with desired styrene units in theelastomer segment are very useful in making gels with improved elasticrecovery under cyclic loading conditions at or near 100% strain. Thisreduces their viscosity and makes them easier to process. The styrenecontent tapers down from very little at the ends of the elastomersegment to a higher concentration in the middle the EB/S represents astyrene/ethylene/butylene copolymer segment with the maximum styrenecontent in the center. CD polymers having Tg of −55° C., −54° C., −53°C., −52° C., −51° C., −50° C., −49° C., −48° C., −47° C., −46° C., −45°C., −44° C., −43° C., −42° C., −41° C., −40° C., −39° C., −38° C., −37°C., −36° C., −35° C., −34° C., −33° C., −32° C., −31° C., −30° C., −29°C., −28° C., −27° C., −26° C., −25° C., −24° C., −23° C., −22° C., −21°C., −20° C., −19° C., −18° C., −17° C., −16° C., −15° C., −14° C., −13°C., −12° C., −11° C., −10° C. and the like are useful in making the gelarticles of the present invention. CD polymers with polystyrene contentof from about 30% to about 65% are useful in forming the gel articles ofthe invention, including about 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%,37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%. 47%, 48%, 49%, 50%,51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%,65%, 66%, 67%, about 68%. CD polymers with calculated midblock PSC % offrom about 25% to about 50% are useful in forming the gel articles ofthe invention, including about 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%,32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%,46%. 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, about 55%.

Other representative examples of commercially available elastomersuseful in forming gels of the invention include: Shell Kratons D1101,D1102, D1107, D1111, D1112, D1113X, D1114X, D1116, D1117, D1118X,D1122X, D1125X, D1133X, D1135X, D1184, D1188X, D1300X, D1320X, D4122,D4141, D4158, D4240, G1650, G1652, G1657, G1701X, G1702X, G1726X,G1750X, G1765X, FG1901X, FG1921X, D2103, D2109, D2122X, D3202, D3204,D3226, D5298, D5999X, D7340, G1654X, G2701, G2703, G2705, G1706, G2721X,G7155, G7430, G7450, G7523X, G7528X, G7680, G7705, G7702X, G7720,G7722X, G7820, G7821X, G7827, G7890X, G7940, G1730 (SEPSEP), FG1901× andFG1921X. Kuraray's SEPS, SEP/SEPS or SEP/SEB/SEPS Nos. SEP 1001, SEP1050, 2027, 2003, SEPS 2006, SEPS 2023, SEPS 2043, SEPS 2063, SEPS 2050,SEPS 2103, SEPS 2104, SEPS 2105, SEBS 8004, SEBS 8007, H-VS-3 (S-V-EP-S)and the like.

Typical representative Dow poly(ethylene-styrene) random copolymers(interpolymers) produced by metallocene catalysts, using single site,constrained geometry addition polymerization catalysts resulting inpoly(ethylene-styrene) substantially random copolymers include ESI-#1thru #38, including ES16, ES24, ES27, ES28, ES28, ES30, ES44 withstyrene wt % of about 15.7, 23.7, 27.3, 28.1, 39.6 & 43.9 respectively,M copolymers (ES53, ES58, ES62, ES63, and ES69 with styrene wt % ofabout 52.5, 58.1, 62.7, 62.8, and 69.2 respectively and crystallinity,%, DSC, based on copolymer of about 37.5, 26.6, 17.4, 22.9, 19.6 and 5.0respectively), S copolymers (ES72, ES73, and ES74 with styrene wt % ofabout 72.7, 72.8, and 74.3 respectively). Other grade copolymers includeES60 (melt index 0.1, 0.5, 3, 10), ES20 (MI=0.1, 0.5, 3, 11).

Theory notwithstanding, the multiblock copolymer gel properties can beattributed to the additional blocks affecting the separate polymerphases, the additional blocks affecting the heterophase structure, theadditional blocks affecting the interfacial regions between phases ofthe multiblock polymers, the additional blocks forming a separate phaseor inducing the formation of additional separate phases, or the highmolecular weight and combination of high styrene content of the blockcopolymer. Due to the additional number of midblocks of the copolymers,the differences in solubility parameters between (A) and (B) becomesgreater than the solubility parameters differences between (A) and (B)of triblock copolymers, where B denotes the lone midblock polymer chain.Moreover, the presence of additional midblocks of ethylene, propylene,butylene, ethylene-propylene, or ethylene-butylene may contribute tostress-induced crystallization. This may explain why as the viscosity ofthe multiblock copolymers is increased to a higher level, the appearanceof the invention gels change from clear to more translucent white.

The invention gels containing one or more SEEPS and SEB-EB/SEBScopolymers in combination with or without other polymers can resisttearing (by almost any desire selected degrees) under tensile loads ordynamic deformation in that when cut or notched, the “crack” made on thegel deep surface does not readily propagate further under dynamicdeformation or tensile loads. Unlike triblock copolymer gels, such ascertain certain (SEBS) and (SEPS) gels which possess high tensilestrength and will catastrophically snap apart into two reflective cleansmooth surfaces when cut or notched under tensile or dynamic loads.Furthermore, when elongated, the invention gels can exhibit two or moredraw plateaus and can possess high tensile strength and rapid returnfrom high extension without noticeable set or deformation. As observed,the invention gels can be stretched by a first tensile load with uniformdeformation to a measured length, upon the application of higher tensileloads, the gel can be further extended without breaking. Upon release,the gel returns immediate to its original shape and any necking quicklydisappears. Again, theory notwithstanding, the additional drawingplateaus of the gel may be attributed to yielding of crystalliteformations ethylene or propylene components in the gel or yield ofinduced interfacial regions of concentrated ethylene or propylenebetween the domains which during extension absorbs the elastic energy.Likewise, the resistance to tear propagation of the invention gels whennotched under tensile load can be attributed to yielding of the gelmidblock components, yielding of additional phases, or yielding ofinterfacial regions before rupture or deformation of the (A) domains cantake place.

Additionally, shearing, heating or cooling form the molten state canalter the gels' state. The invention gels can be made to exhibit longelastomeric recovery times. Such gels can be used effectively insuppressing low frequency vibrations and for absorbing energy. Theunusual properties of the invention gels can be attributed to alteringdifferent phase or interfacial arrangements of the domains of themultiblock copolymers.

These gels can exhibit a larger unit lateral contraction at the sameelongation per unit of length as their counterpart parent gels fromwhich the invention gels are derived or formed. This property wouldallow a same unit volume of gel when elongated as its parent to easilywedge between the teeth when flossing. It would seem that a gel havingthe 1.0 cm3 volume made from a ratio of 100 parts by weight of copolymerand 400 parts plasticizer would have a unique macro volumeconfigurations that is at equilibrium with the plasticizer which is muchlike a 3-D fingerprint which is uniquely different from any other gel ofa different copolymer to plasticizer ratio. Reducing the plasticizercontent of a ratio 100:400 gel to a 100:300 ratio of copolymer toplasticizer will decrease the amount of plasticizer, but the originalmacro volume configurations will remain the same.

Speculative theories not withstanding, configurations may take the formof (1) swiss cheese, (2) sponge, (3) the insides of a loaf of bread, (4)structures liken to ocean brain corals, (5) large structures and smallstructures forming the 3-D gel volume landscape, (6) the outer heatedsurface which cools faster than the inner volumes of the gel during itscooling histories may have a patterned crust (rich in A micro-phases)like that of a loaf of bread and the inner volume may have much like1-5, and (7) the many different possible structures are unlimited andvolume landscapes may be interconnected at the macrolevel by threads ormicro-strands of B micro-phases.

The amount of plasticizer extracted can advantageously range from lessthan about 10% by weight to about 90% and higher of the total weight ofthe plasticizer. More advantageously, the extracted amounts ofplasticizer can range from less than about 20% by weight to about 80% byweight of the total plasticizer, and still more advantageously, fromabout 25% to about 75%. Plasticizing oils contained in the inventiongels can be extracted by any conventional methods, such as solventextraction, physical extraction, pressure, pressure-heat, heat-solvent,pressure-solvent-heat, vacuum extraction, vacuum-heat extraction,vacuum-pressure extraction, vacuum-heat-pressure extraction,vacuum-solvent extraction, vacuum-heat-solvent-pressure extraction, etc.The solvents selected, may be solvents which do not substantiallydisrupt the A and B phases of the copolymers forming the invention gels.Any solvent which will extract plasticizer from the gel and do notdisrupt the A and B phases can be utilized. Suitable solvents includealcohols, primary, secondary and tertiary alcohols, glycols, etc.,examples include methanol, ethanol, tetradecanol, etc. Likewise, thepressures and heat applied to remove the desired amounts of oils shouldnot be sufficient to disrupt the A and B domains of the copolymers. Toform a lower rigidity gel, the simplest method is to subject the gel toheat in a partial vacuum or under higher vacuum for a selected period oftime, depending on the amount of plasticizer to be extracted.

Surprisingly, as disclosed in my application S Ser. No. 09/896,047 filedJun. 30, 2001, oil extraction from the invention gels can be achievedwith little or no energy in the presence of one or more silicone fluidsto almost any degree. A theory can be made to explain the physicsinvolved in the extraction process which reasoning is as follows: (1)When water is placed in contact with an oil extended gel, the gel willnot over time exhibit weight loss. (2) When oil is add to a column ofwater in a test tube, the oil will separate out and find its level abovethe column of water. (3) The surface tension of water at 25° C. is about72.0 mN/m. (4) The surface tension of oil (mineral oil) at 25° C. isabout 29.7 mN/m. (5) The surface tension of silicone fluid at 25° C.range from abut 16 to abut 22 mN/m (for example: the surface tension of100 cSt silicone fluid at STP is 20.9 mN/m). (6) The density of oil isless than the density of silicone fluid, silicone grease, silicone gel,and silicone elastomer. (7) Oil is not a polar liquid and is highlycompatible with the rubber phase of the oil gel forming polymer. (8)Silicone is polar and not compatible with the polymer's rubber phase.

The molecules of a liquid oil drop attract each other. The interactionsof an oil molecule in the liquid oil drop are balanced by an equalattractive force in all directions. Oil molecules on the surface of theliquid oil drop experience an imbalance of forces at the interface withair. The effect is the presence of free energy at the surface. Thisexcess energy is called surface free energy and is quantified as ameasurement of energy/area. This can be described as tension or surfacetension which is quantified as a force/length measurement or m/Nm.

Clearly gravity is the only force pulling on the extracted oil from thegel in the presence of silicone fluid at the gel-petri dish interface inthe examples below. In the case of gel samples in the petri dishes incontact with silicone fluids, the extracted oil are collected on the topsurface layer of the silicone fluid while the silicone fluid maintainconstant contact and surrounds the gel sample. In the case of gel placedin a test tube of silicone fluid of different viscosity, the oil isextracted and migrates and collect at the top of the silicone fluidsurface while the gel reduces in volume with time. The oil extractionprocess in silicone is accompanied by buoyant forces removing theextracted oil from the surroundings of the gel constantly surroundingthe gel with fresh silicone fluid while in the example of alcohol, sincethe oil is heavier, the oil is maintained and surrounds the gel sampleforming a equilibrium condition of oil surround the gel sample whilekeeping the alcohol from being in contact with the gel sample. Thereforein order to use alcohol to extract oil from a gel sample, the extractedoil must be constantly removed from the oil alcohol mixture as is thecase during soxhlet extraction which process requires additional energyto pump the oil-alcohol mixture away from the sample and removing theoil before forcing the alcohol back to the gel sample surface to performfurther extraction.

Silicone fluid is efficient and useful for extracting oil form oil gelcompositions with the assistance of gravity and buoyancy of oil in thesilicone fluids. It is very difficult to extract, separate, or removeoil from an oil gel composition by positive or vacuum pressure or heatwhile using little or no energy and because of the affinity of therubber midblock for oil, not even the weight of a two ton truck restingon a four square foot area (placing a layer of gel between four pairs ofone foot square parallel steel plates one set under each of the trucktire resting on the gels) can separate the oil from the gel composition.The use of silicone fluids of various viscosity acts as a liquid semiporous membrane when placed in constant contact with an oil gelcomposition will induce oil to migrate out of the gel composition. Bythe use of gravity or oil buoyancy, no energy is required to run the oilextraction process.

The invention gels, invention gel composite articles can have two ormore rigidity regions made by the plasticizer extraction methods of theinvention, said gel rigidity regions having no physically separableboundaries. The denoted by G having one or two or more rigidity regionscan be in contact with a selected material M or in combination with oneor more of a different gel forming a composite of the combination GnGn,GnGnGn, GnMn, GnMnGn, MnGnMn, MnGnGn, MrtMnMnGnMn, MnGnGnMn, GnMnGnGn,GnGnMnMn, GnMnMnGn, GnGnMnGnMnGnGn, GnMnGnMrMn, MnGnMnGnMnGn,GnGnMnMnGn, GnGnMnGnMn, GnGnMnGnMnGn, GnMnGnMnGn, MnMnMnGn or apermutation of one or more of said Gn with Mn; wherein when n is asubscript of M, n is the same or different selected from the groupconsisting of paper, foam, plastic, fabric, metal, metal foil, concrete,wood, glass, glass fibers, ceramics, synthetic resin, synthetic fibersor refractory materials; and wherein when n is a subscript of G, ndenotes a different gel rigidity.

In the case of one embodiment of the invention gels made in the shape ofa fishing bait in contact with silicone fluid, the elastomer or rubberbeing highly compatible with the oil, holds the oil in place within theboundary of the rubber molecular phase. It is this affinity of therubber and oil molecules and the attraction of oil molecules for eachother that prevents the oil from bleeding out of the surface of the gelbody. There exist then, at the surface of the gel several types ofsurface tensions of: (iii) oil-air surface tension, (iv) oil-rubbersurface tension, (v) rubber-air surface tension, (vi) rubber/oil-airsurface tension, and (vii) rubber-rubber surface tension. Other forcesacting on the gel are: the elastic force of the polymer network pullinginwards, similar to stretched out rubber bands, which is in equilibriumwith the oil molecules' attraction to the rubber molecules of thepolymer network. In the case of SBS, the lower compatibility of themidblock butadiene with oil, once a gel is made, the SBS networkimmediately contracts due to elastic forces to produce oil bleedingwhich is evidence of the poor compatibility of the rubber block for theoil molecules.

The intermolecular forces that bind similar molecules together arecalled cohesive forces. Intermolecular forces that bind a substance to asurface are called adhesive forces. When two liquids are in contact suchas oil and silicone fluid, there is interfacial tension. The more densefluid is referred to herein as the “heavy phase” and the less densefluid is referred to as the “light phase”. The action at the surface ofthe oil extended polymer gel surface when brought into contact withsilicone fluid is as follows: a drop of silicone fluid when placed onthe flat surface of a oil extended polymer gel will wet the gel surfaceand spread over a larger area as compared to a drop of oil placed on thesame gel surface. Because the surface free energy of the silicone fluidin contact with the gel surface is lower than the surface free energy ofthe oil, the silicone fluid has the ability to displaces the oil fromthe surface of the gel. Various block copolymers described above andbelow can be obtained which are amorphous, highly rubbery, andexhibiting minimum dynamic hysteresis.

Block copolymer S-EB-S: the monomer butadiene can be polymerized in aether/hydrocarbon solvent to give a 50/50 ratio of 1,2poly(butadiene)/1,4 poly(butadiene) and on hydrogenation no long runs of—CH₂— groups and negligible crystallinity, ie, about (0.5)₄ or 0.06 or6% and actual crystallinity of about 3%. Due to the constraints of Tgand minimum hysteresis, conventional S-EB-S have ethylene-butyleneratios of about 60:40 with a crystallinity of about (0.6)₄ or 0.129 or12% and actual crystallinity of about 7.7%. Block copolymer S-EP-S: themonomer isoprene when polymerized will produce 95% 1,4 poly(isoprene)/5%3,4 poly(isoprene) and upon hydrogenation will form amorphous, rubberypoly(ethylene-propylene) midblock and no long runs of —CH₂— and nocrystallinity. Mixed block copolymer S-EB/EP-S: the polymerization of a50/50 mixture of isoprene/butadiene monomers in suitableether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4poly(butadiene) on hydrogenation will produce a maximum crystallinity of(0.25)₄ or 0.4%. The actual crystallinity would be approximately about0.2%, which is negligible and results in a good rubbery midblock. Thepolymerization of a 80/20 mixture of isoprene/butadiene monomers insuitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4poly(butadiene) will upon hydrogenation produce a low crystallinity of(0.10)₄ or 0.01%. The actual crystallinity would be approximately about0.006%, which is negligible and results in a good rubbery midblock. Thepolymerization of a 20/80 mixture of isoprene/butadiene monomers insuitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4poly(butadiene) will upon hydrogenation produce a low crystallinity of(0.4)₄ or 2.56%. The actual crystallinity would be approximately about1.53%, which is negligible and results in a good rubbery midblock.

Block copolymer S-EEP-S: the polymerization of a 20/80 mixture ofisoprene/butadiene monomers in suitable ether/hydrocarbon solvents togive a 40:60 ratio of 1,2 and 1,4 poly(butadiene) will uponhydrogenation produce a low crystallinity of (0.48)₄ or 5.3%. The actualcrystallinity would be approximately about 3.2%, which is negligible andresults in a good rubbery midblock. This theoretical % of actualcrystallinity corresponds well to commercially available SEEPS Septon4033 and 4055 which varies with batch lots.

These values are all negligible. There will be very little or nodetectable crystallinity in any of these polymer midblocks. In a mixedether/hydrocarbon solvent, values will be intermediate, depending on theratio of ether to hydrocarbon. The midblock components (B) of theinvention gels can comprise various combinations of midblocks betweenthe selected end blocks (A); these include:-E-EB-, -E-EP-, -E-EP-E-,-E-EB-E-, -E-E-EP-, -E-E-EB-, -E-EP-, -EB-EB/S-EB-, -EB-EB-, and-EB-EB/S- and the like.

The (B) midblock of two or more polymer chains can be obtained byhydrogenation methods, for example: 1,4 polybutadiene (B1,4) can beconverted by hydrogenation to poly(ethylene), 1,4-polybutadiene (B1,4)and 1,2-polybutadiene (B1,2) can be converted by hydrogenation topoly(ethylene-butylene), 1,4-poly-isoprene (11,4) can be converted byhydrogenation to poly(ethylene-propylene), 1,2-polybutadiene (B1,2) canbe converted by hydrogenation to atactic poly(1 -butene)(polybutylene),1,4-polybutadiene (B1,4) and polyisoprene (1) 1,4-poly-butadiene (B1,4)can be converted by hydrogenation topoly(ethylene-ethylene-co-propylene-ethylene),2-methyl-1,3-polybutadiene and 1,3-polybutadiene (1, B1,3) can beconverted by hydrogenation to poly(ethylene-ethylene-co-propylene), andthe like. Polypropylene can be modified by tailblocking apoly(ethylene-propylene) copolymer segment on the propylene block toform poly(propylene-ethylene-co-propylene); likewise,poly(ethylene-propylene)_(n) (EP),poly(propylene-ethylene-co-propylene-propylene) (P-EP-P),poly(propylene-ethylene-propylene) (P-E-P),poly(ethylene-ethylenepropylene) (E-EP) can be formed. It is notedherein that B (bold) denotes polybutadiene and B (plain) denotespolybutylene.

Further, the multiblock copolymers (A_(n)-B-A_(n)) can be obtained byvarious synthesis methods including hydrogenation of selected blockcopolymers. When the subscript n of A is =1, (polystyrene) (S), forexample, suitable block copolymers can be converted to the usefulmultiblock copolymers forming the invention gels. These include:conversions of S-1-B1,3-S to (S-E-EP-S), S-B1,41-B1,4S to (S-E-EP-E-S),S-B1,2-1-S to (S-B-EP-S), S-B1,3-B1,2-B1,4S to (S-E-EB-S),S-B1,4B1,2-1-S to (S-EB-EP-S), S-1-B1,3-B1,2-B1,4S to (S-E-EP-EB-S),etc. As denoted herein abbreviations are interchangeably used, forexample, (S-E-EP-S) denotespoly(styrene-ethylene-ethylene-co-propylene-styrene). Other linearmultiblock copolymers (denoted in abbreviations) can be formed,including (S-B-EB-S), (S-E-EB-E-S), (S-B-EP-E-S), (S-B-EB-B-S),(S-E-E-EP-S), (S-E-E-EB-S), and the like.

The multiblock star-shaped (or radial) copolymers (An-B)n can beobtained by various synthesis methods including hydrogenation ofselected block copolymers. When the subscript n of A is =1,(polystyrene) (S), for example, suitable block copolymers can beconverted to the useful multiblock copolymers forming the inventiongels. These include: conversions of (S-1-B1,3)_(n) topoly(styrene-ethylene-ethylene-co-propylene)_(n) denoted by theabbreviation (S-E-EP)_(n), (S-B1,4-1-B1,4)_(n) to (S-E-EP-E)n,S-B1,2-I)n to (S-B-EP)n, (S-B1,3-B1,2-B1,4)n to (S-E-EB)_(n),(S-B1,4-B1,2-I)n to (S-EB-EP) n, (S-1-B1,3-B1,2-B1,4)n to (S-E-EP-EB)n,etc. Other multiblock copolymers can be formed, including: (S-B-EB)n,(S-E-EB-E)n, (S-B-EP-E)n, (S-B-EB-E)n, (S-B-EP-B)n, (S-B-EB-B)n,(S-E-E-EP)n, (S-E-E-EB)n, (S-B-E-EP)n, (S-B-E-EB)n, (S-B-B-EP)n,(S-B-B-EB)n, (S-E-B-EB)n, (S-E-B-EP)n, (S-EB-EB)n, (S-EP-EP)n,(S-E-EB-EB)n, (S-E-EP-EP)n, (S-E-EB-EP)n, (S-B-EB-EB)n, (S-B-EP-EP)n,and the like.

The B and A portions of the linear and star-shaped multiblock copolymersare incompatible and form a two or more-phase system consisting ofsub-micron glassy domains (A) interconnected by flexible B chains. Thesedomains serve to crosslink and reinforce the structure. This physicalelastomeric network structure is reversible, and heating the polymerabove the softening point of the glassy domains temporarily disrupt thestructure, which can be restored by lowering the temperature. It shouldbe noted that when the A to B ratios falls substantially below about30.70, various properties such as elongation, tensile strength, tearresistance and the like can decrease while retaining other desiredproperties, such as gel rigidity, flexibility, elastic memory.

The Kuraray SEPTON 4000 series block polymers: 4033, 4044, 4045, 4055,4077, 4099, Kraton GA: RP6936, and the like useful in making the gels ofthe instant invention are made from hydrogenated styreneisoprene/butadiene styrene block copolymer or more specifically madefrom hydrogenated styrene block polymer with 2-methyl-1,3-butadiene and1,3-butadiene. Such poly(styrene-isoprene/butadiene-styrene) polymers,depending on the butadiene structure, when hydrogenated will result in“(SEB/EPS)” or reading the other way “(SEP/EBS)”. In cases where thebutadiene structures are controlled, it is appropriate to denote(SEB/EPS) as (SE/EPS) where E/EP is ethylene-ethylene-propylene or moresimply as (SEEPS) to indicate that the ethylene (E) of theethylene-butylene (EB) segment of the midblock (EB/EP) of the (SEB/EPS)block polymer is substantially greater than butylene (B) and the amountof (E) can be sufficient so as to exhibit ethylene crystallinity. Thecontrolled distribution S-EB-EB/S-EB-S block copolymer can be made byvarying the relative amount of the distribution agent which creates thecontrolled distribution of the mono alkenyl arene and conjugated diene,and also controls the microstructure of the conjugated diene which istaught in US Patent No. Re 27145, and above cited applications Nos.60/355,210 filed Feb. 7, 2002, Ser. No. 10/359,462 filed Feb. 6, 2003,and Ser. No. 10/745,352 filed Dec. 22, 2003.

At 10 weight percent SEEPS 4055 is about 5,800 mPa·s and higher. Otherlinear and star multiblock copolymers such as (S-E-EP-S), (S-E-EP-E-S),(S-B-EP-S), (S-E-EB-S), (S-EB-EP-S), (S-E-EP-EB-S), (S-B-EB-S),(S-E-EB-E-S), (S-B-EP-E-S), (S-B-EB-E-S), (S-B-EP-B-S), (S-B-EB-B-S),(S-E-E-EP-S), (S-E-E-EB-S), (S-B-E-EP-S), (S-B-E-EB-S), (S-B-B-EP-S),(S-B-B-EB-S), (S-E-B-EB-S), (S-E-B-EP-S), (S-EB-EB-S), (S-EP-EP-S),(S-E-EB-EB-S), (S-E-EP-EP-S), (S-E-EB-EP-S), (S-B-EB-EB-S),(S-B-EP-EP-S), (S-B-EB-EP-S), (S-B-EP-EB-S), (S-E-EP-E-EP-S), (S-E-EP)n,(S-E-EP-E)n, (S-B-EP)n, (S-E-EB-S)n, (S-EB-EP-)n, (S-E-EP-EB)n,(S-B-EB)n, (S-E-EB-E)n can also exhibit viscosities at 5 weight percentsolution in toluene at 30° C. of from less than about 100 to about 200,300, 400, 500, 600, 700, 800, 900, 1,000, 1,200, 1,300, 1,600, 1,800,2,000 mPa·s and higher.

The copolymer forming the invention gels can have a broad range of A endblock to B center block ratio of about 20:80 or less to about 40:60 orhigher. The A:Z weight ratios can range from lower than about 20:80 toabove about 40-60 and higher. More specifically, the values can be19:81, 20:80, 21:79, 22:78, 23:77, 24:76, 25:75, 26:74, 27:73, 28:72,29:71, 30:70, 31:69, 32:68, 33:67, 34:66, 35:65, 36:64, 37:63, 38:62,39:61, 40:60, 41:59, 42:58, 43:57, 44:65, 45:55, 46:54, 47:53, 48:52,49:51, 50:50, 51:49 and etc. Other ratio values of less than 19:81 orhigher than 51:49 are also possible. Broadly, the styrene block toelastomeric block ratio A:Z of the high viscosity multiblock and starcopolymers is about 20:80 to about 40:60 or higher, less broadly about31:69 to about 40:60, preferably about 32:68 to about 38:62, morepreferably about 32:68 to about 36:64, particularly more preferablyabout 32:68 to about 34:66, especially more preferably about 33:67 toabout 36:64, and most preferably about 30:70.

In general, for these block copolymers, the various measured viscositiesof 5, 10, 15, and 20, weight percent solution values in toluene at 30°C. can be extrapolated to a selected concentration. For example, asolution viscosity of a 5 weight percent copolymer solution in toluenecan be determined by extrapolation of 10, 15, and 20 weight percentmeasurements to 5 weight percent concentration.

The Brookfield Viscosities can be measured at various neat polymerconcentrations, for example, the selected high viscosity linearmultiblock copolymers in can have a typical Brookfield Viscosity valueof a 20 weight percent solids solution in toluene at 25° C. of about1,800 cps and higher, and advantageously about 2,000 cps and higher.Typically, the Brookield Viscosity values can range from at least about1,800 to about 16,000 cps and higher. More typically, the BrookfieldViscosity values can range from at least about 1,800 cps to about 40,000cps and higher. Still more typically, the Brookfield Viscosity valuescan range from at least about 1,800 cps to about 80,000 cps and higher.Due to structural variations between the multiblock and star-shapedcopolymers, the high viscosity star-shaped or radial copolymers,typically, may exhibit a lower Brookfield Viscosity value than itscounterpart linear multiblock copolymers. However, when the multiblockcopolymers are considered as star-shaped or branched, than at equalbranch lengths, the solution viscosities of the multiblock copolymersand branched copolymers are about the same or equivalent In all cases,the molecular chain lengths (molecular weights) of the multiblock andstar-shaped (or radial) copolymers must be sufficient to meet the highsolution Brookfield Viscosities requirements described herein that isnecessary for making the soft, strong and extreme tear resistant gels.The copolymers selected have Brookfield Viscosity values ranging fromabout 1,800 cps to about 80,000 cps and higher when measured at 20weight percent solution in toluene at 25° C., about 4,000 cps to about40,000 cps and higher when measured at 25 weight percent solids solutionin toluene. Typical examples of Brookfield Viscosity values forstar-shaped copolymers at 25 weight percent solids solution in tolueneat 25° C. can range from about 3,500 cps to about 30,000 cps and higher;more typically, about 9,000 cps and higher. Other advantageousmultiblock and multiblock star-shaped copolymers can exhibit viscosities(as measured with a Brookfield model RVT viscometer at 25° C.) at 10weight percent solution in toluene of about 400 cps and higher and at 15weight percent solution in toluene of about 5,600 cps and higher. Otheradvantageous multiblock and star-shaped copolymers can exhibit about8,000 to about 20,000 cps at 20 weight percent solids solution intoluene at 25° C. Examples of most advantageous high viscosity linearmultiblock copolymers can have Brookfield viscosities at 5 weightpercent solution in toluene at 30° C. of from about 40 to about 50, 60,70, 80, 90, 100 . . . 120, 150, 200 cps and higher, while viscosities ofstar-shaped multiblock copolymers are 150 cps and higher.

Examples of high viscosity multiblock copolymers having two or moremidblocks are Kuraray's (S-E-EP-S) Septon 4033, 4044, 4045, 4055, 4077,4099, and the like (hydrogenated styrene isoprene/butadiene blockcopolymers) more specifically, hydrogenated styrene block polymer with2-methyl-1,3-butadiene and 1,3-butadiene. Kuraray's 4044 (S-E-EP-S)multiblock copolymer and 4099 exhibit viscosities at 7.5 and 2.5 weightpercent solution in toluene at 30° C. of about 97 mPa·s and about 23mPa·s with about a typical specification tolerances of about 100 +/−20and 20 +/−10 respectively. Kuraray's 4055 (S-E-EP-S) multiblockcopolymer and 4077 exhibit viscosities at 5 weight percent solution intoluene at 30° C. of about 90 cps to about 120 mPa·s and about 200 toabout 380 mPa·s respectively.

The star-shaped copolymers are characterized as having a BrookfieldViscosity value at 5 weight percent solids solution in toluene at 30° C.of from about 150 mPa·s to about 380 mPa·s and higher, advantageouslyfrom about 150 mPa·s to about 260 mPa·s and higher, more advantageouslyfrom about 200 mPa·s to about 580 mPa·s and higher, and still moreadvantageously from about 500 mPa·s to about 1,000 mPa·s and higher.

The presence of polyethylene and crystallinity in block copolymers canbe determined by NMR and DSC. Physical measurements (NMR and DSC) oftypical commercial Kraton G 1651, Septon 2006, Septon 4033 and Septon4055 block were performed. Two types of ¹³C NMR spectra data werecollected. The gated decoupled experiment provided quantitative data foreach type of carbon atom. The DEPT experiment identified each type ofcarbon atom having attached protons. The DEPT data allowed assignment ofthe resonances in the gated decoupled experiment, which was thenintegrated for quantitation of the different types of midblock and endgroups in each polymer tested

The relative quantities of each type of carbon group in the variouspolymers were found. The uncertainty associated with these measurementsis estimated as +3 percentage units. Only the Kraton 1651 spectrum hadresonances below about 20 ppm. These resonances, at 10.7-10.9 ppm, wereassigned to the butylene methyl group and distinguish the SEBS polymerfrom the SEPS and SEEPS types of polymer (36). Only the Septon 2006spectrum lacked the resonance at about 20 ppm that is characteristic ofpolyethylene units (defined here as three contiguous CH₂ groups), andthis feature distinguishes the SEPS polymer from the SEBS and SEEPSpolymers (36). There were additional differences between the spectra.The Septon 2006 and the Septon 4033 and 4055 spectra all showedresonances at 20 ppm; whereas the spectrum of Kraton 1651 was missingthis resonance. The 20 ppm peak is characteristic of the methyl group ofa propylene subunit, which is present in SEPS and SEEPS polymers butabsent in the SEBS polymer. There were also a methylene peak, at 24.6ppm, and a methine peak at 32.8 ppm, in all of the Septon spectra butnot in the Kraton 1651 spectra. These resonances also arise from thepropylene subunit.

The chemical shifts, relative intensities, and relative integrationswere the same for the spectra of the Septon 4033 and Septon 4055,indicating that these two polymeric compositions are identical based onNMR spectroscopy. DSC of ASTM D3417-99 was modified to provideconditions for the samples to have the best possible chance to exhibitany crystallinity. The protocol was as follows: (1) heat to 140° C. @10° C./min., (2) cool to 0° C. @ 2° C./min., (3) place in freezer for 1week (4) heat to 140° C. @ 1° C./min, and (5) cool to 0° C. @ 1° C./min.

This protocol was used with the exception that the samples were left inthe freezer for approximately 2 months, instead of 1 week, because theDSC equipment broke during the week after the first run and requiredsome time for repair. This delay is not expected to have negativelyimpacted the results of the experiment.

Two HDPE reference samples gave clearly defined crystallizationexotherms and fusion endotherms, allowing calculation of heats ofcrystallization and fusion. These results showed that the equipment andmethodology were fully functional, and this check was performed dailyduring DSC operation. Of the samples, only Kraton 1651 showeddiscernable transitions for both crystallization and fusion. The Septon2006 showed no discernable transitions, which is consistent with itsSEPS structure being entirely amorphous. The Septons 4033 and 4055showed crystallization exotherms.

The heats of crystallization for the Kraton 1651 and Septons 4033 and4055 were small, below about 3 J/g, indicating that small amounts ofcrystallinity are present in these polymers. The DSC data show:

-   -   Kraton 1651: crystallization exotherm peak at 18.09° C.,        crystallization exotherm-mass normalized enthalpy (J/g) of 1.43,        fusion endortherm peak at 34.13° C., and Fusion Endotherm-mass        normalized enthalphy J/g of 15.17.    -   Septon 2006: crystallization exotherm peak (not detected),        crystallization exotherm-mass normalized enthalpy (not        detected), fusion endortherm peak NONE, and Fusion        Endotherm-mass normalized enthalphy (not detected).    -   Septon 4033: crystallization exotherm peak at 2.86° C.,        crystallization exotherm-mass normalized enthalpy (J/g) of 3.00,        fusion endortherm peak (not detected), and Fusion Endotherm-mass        normalized enthalphy (not detected).    -   Septon 4055: crystallization exotherm peak at 14.4° C.,        crystallization exotherm-mass normalized enthalpy (J/g) of 1.32,        fusion endortherm peak (not detected), and Fusion Endotherm-mass        normalized enthalphy (not detected).    -   Aldrich 13813JU polyethylene reference: crystallization exotherm        peak at 119.72° C., crystallization exotherm-mass normalized        enthalpy (J/g) of 174.60, fusion endortherm peak at 130.70° C.,        and Fusion Endotherm-mass normalized enthalphy J/g of 189.90.

The Brookfield Viscosity of a 5 weight percent solids solution intoluene at 30° C. of 2006 is about 27. Typical Brookfield Viscosities ofa 10 weight percent solids solution in toluene at 30° C. of Kuraray SEP1001, SEP 1050, SEPS 2007, SEPS 2063, SEPS 2043, SEPS 2005, SEPS 2006,are about 70, 70, 17, 29, 32, 50, 1200, and 1220 respectively. TypicalBrookfield Viscosity of a 25 weight percent solids solution in tolueneat 25° C. of Kraton D1101, D1116, D1184, D1300X, G1701X, G1702X areabout 4000, 9000, 20000, 6000, 50000 and 50000 mPa·s respectively.Typical Brookfield Viscosity of a 10 weight percent solids solution intoluene at 25° C. of G1654X is about 370 cps. The Brookfield Viscositiesof a 20 and 30 weight percent solids solution in toluene at 30° C. ofH-VS-3 are about 133 mPa·s and 350 mpa·s respectively. Other polymerssuch as, thermoplastic crystalline polyurethane copolymers withhydrocarbon midblocks can also be employed.

The glassy A component type homopolymers can be advantageously added toprovide non-tackiness which are selected from one or more homopolymersof: polystyrene, poly(alpha-methylstyrene), poly(o-methylstyrene),poly(m-methylstryene), poly(p-methylstyrene), and poly(dimethylphenyleneoxide) (GE PPO 612 and Arizona XR 6504). Such glassy polymers can be usein forming the invention gel, but would increase hot tack.

The average molecular weight of the glassy homopolymers useful in theinvention gels advantageously can range from about 2,500 to about90,000, typical about 3,000; 4,000; 5,000; 6,000; 7,000; 8,000; 9,000;10,000; 11,000; 12,000, 13,000; 14,000; 15,000; 16,000; 17,000; 18,000;19,000; 20,000; 30,000; 40,000; 50,000; 60,000; 70,000; 80,000; 90,000and the like. Example of various molecular weights of commerciallyavailable polystyrene: Aldrich Nos.: 32,771-9 (2,500Mw), 32,772-7 (4,000Mw), 37,951-4 (13,000 Mw), 32-7743 (20,000 Mw), 32,775-1 (35,000 Mw),33,0345 (50,000 Mw), 32,777-8 (90,000 Mw); poly(alpha-methylstyrene)#41,794-7 (1,300 Mw), 19,184-1 (4,000 Mw); poly(4 methylstyrene)#18,227-3 (72,000 Mw), Endex 155, 160, Kristalex 120, 140 from HerculesChemical, GE: Blendex HPP820, HPP822, HPP823, and the like.

Suitable triblock copolymers and their typical viscosities are furtherdescribed: styrene-ethylene-butylene-styrene block copolymers (SEBS)available from Shell Chemical Company and Pecten Chemical Company(divisions of Shell Oil Company) under trade designations Kraton G 1651,Kraton G 1654×, Kraton G 4600, Kraton G 4609 and the like. ShellTechnical Bulletin SC: 1393-92 gives solution viscosity as measured witha Brookfield model RVT viscometer at 25° C. for Kraton G 1654×at 10%weight in toluene of approximately 400 mPa·s and at 15% weight intoluene of approximately 5,600 cps. Shell publication SC:68-79 givessolution viscosity at 25° C. for Kraton G 1651 at 20 weight percent intoluene of approximately 2,000 cps. When measured at 5 weight percentsolution in toluene at 30° C., the solution viscosity of Kraton G 1651is about 40. Examples of high viscosity SEBS triblock copolymersincludes Kuraray's SEBS 8006 which exhibits a solution viscosity at 5weight percent at 30° C. of about 51 cps. Kuraray's 2006 SEPS polymerexhibits a viscosity at 20 weight percent solution in toluene at 30° C.of about 78,000 cps, at 5 weight percent of about 27 cps, at 10 weightpercent of about 1220 cps, and at 20 weight percent 78,000 cps. KuraraySEPS 2005 polymer exhibits a viscosity at 5 weight percent solution intoluene at 30° C. of about 28 cps, at 10 weight percent of about 1200cps, and at 20 weight percent 76,000 cps. Other grades of SEBS, SEPS,(SEB)_(n), (SEP)_(n) polymers can also be utilized in the presentinvention provided such polymers exhibits the required high viscosity.Such SEBS polymers include (high viscosity) Kraton G 1855×which has aSpecific Gravity of 0.92, Brookfield Viscosity of a 25 weight percentsolids solution in toluene at 25° C. of about 40,000 mPa·s or about8,000 to about 20,000 mPa·s at a 20 weight percent solids solution intoluene at 25° C. The styrene to ethylene and butylene (S:EB) weightratios for the Shell designated polymers can have a low range of 20:80or less. Although the typical ratio values for Kraton G 1651, 4600, and4609 are approximately about 33:67 and for Kraton G 1855X approximatelyabout 27:73, Kraton G 1654X (a lower molecular weight version of KratonG 1651 with somewhat lower physical properties such as lower solutionand melt viscosity) is approximately about 31:69, these ratios can varybroadly from the typical product specification values. In the case ofKuraray's SEBS polymer 8006 the S:EB weight ratio is about 35:65. In thecase of Kuraray's 2005 (SEPS), and 2006 (SEPS), the S:EP weight ratiosare 20:80 and 35:65 respectively. Much like S:EB ratios of SEBS and(SEB)_(n), the SEP ratios of very high viscosity SEPS triblockcopolymers are about the same and can typically vary as broadly.

The triblock copolymers such as Kraton G 1654×having ratios of 31:69 orhigher can be used and do exhibit about the same physical properties inmany respects to Kraton G 1651 while Kraton G 1654X with ratios below31:69 may also be use, but they are less advantageous due to theirdecrease in the desirable properties of the final gel.

The high glassy component copolymers suitable for use in forming theinvention gel include high styrene component BASF's Styroflex seriescopolymers including BX 6105 with a statistical SB sequence for the lowelastomeric segments (styrene to butadiene ratio of 1:1) and an overallstyrene content of almost 70%, high styrene content Shell Kraton G,Kraton D-1122×(SB)n, D4122 SBS, D-4240 (SB)n, D4230 (SB)n, DX-1150 SBS,D-4140 SBS, D-1115 SBS, D4222 SBS, Kraton D-1401P, SEBS, Dexco's Vector6241-D, 4411-D, Fina's Finaclear high styrene content SBS seriescopolymers, Phillips Petroleum's XK40 K-Resin styrene/butadienecopolymers, Kuraray's S2104 SEPS. The copolymers include amorphouspolymers with high styrene content SBS, SIS, SEPS, SEB/EPS, and thelike. The copolymers with glassy to elastomeric ratios can range from37:63, 37.6:62.4, 38:62, 39:61, 40:60, 41:59, 42:58, 43:57, 44:65,45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:49 52:48, 53:47, 54:46,55:45, 56:44, 57:43, 58:42, 59:41, 60:40, 6:39, 62:38, 63:37, 64:36,65:35, 66:34, 67:33, 68:32, 69:31, 70:30, 7:29, 72:28, 73:27, 74:26,75:25, 76:24, 77:23, 78:22, 79:21, to 80:20 and higher. High styrenecontent Dow ES30, and ES44 with styrene wt % of 15.7, 23.7, 27.3, 28.1,39.6 & 43.9 respectively, M copolymers (ES53, E58, ES62, ES63, and ES69with styrene wt % of 52.5, 58.1, 62.7, 62.8, and 69.2 respectively andcrystallinity, %, DSC, based on copolymer of 37.5, 26.6, 17.4, 22.9,19.6 and 5.0 respectively, S copolymers ES72, ES73, and ES74 withstyrene wt % of 72.7, 72.8, and 74.3 respectively may also be used.These hard to process polymers can be added (from 0.01 to 30 parts byweight) by dry blending in combination with 200-400 parts oil and withSEEPS 4055, 4033, 4077, 4045, 4044, 4099 and the like and extruded atabout between 75° C.-135° C. to form a pre-blend and then formulatedwith additional oil or/or oil and copolymers to produce the finalinvention gel.

Suitable polyolefins include polyethylene and polyethylene copolymerssuch as Dow Chemical Company's Dowlex 3010, 2021D, 2038, 2042A, 2049,2049A, 2071, 2077, 2244A, 2267A; Dow Affinity ethylene alpha-olefinresin PL-1840, SE-1400, SM-1300; more suitably: Dow Elite 5100, 5110,5200, 5400, Primacor 141-XT, 1430, 1420, 1320, 3330, 3150, 2912, 3340,3460; Dow Attane (ultra low density ethylene-octene-1 copolymers) 4803,4801, 4602, Eastman Mxsten CV copolymers of ethylene and hexene(0.905-0.910 g/cm3).

Plasticizers particularly advantageous for use in practicing the presentinvention are will known in the art, they include rubber processing oilssuch as paraffinic and naphthenic petroleum oils, highly refinedaromatic-free paraffinic and naphthenic food and technical grade whitepetroleum mineral oils, and synthetic liquid oligomers of polybutene,polypropene, polyterpene, etc. The synthetic series process oils arehigh viscosity oligomers which are permanently fluid liquid monolefins,isoparaffins or paraffins of moderate to high molecular weight.

Incorporated herein by reference, in part, is the “Physical and ChemicalProperties of Mineral Oils That Affect Lubrication”, © Copyright HerguthLaboratories, Inc. 1995, which is a review of mineral oils and terms forthe tribologist working in the field of Tribology. A few of the termsare provided for clear reading of the description of the invention asfollows: Viscosity is the property of a fluid that causes it to resistflow, which mechanically is the ratio of shear stress to shear rate.Viscosity may be visualized as a result of physical interaction ofmolecules when subjected to flow. Lubricating oils have long chainhydrocarbon structures, and viscosity increases with chain length. Theunit of absolute or dynamic viscosity is Force/Area × Time. The basic SIunit is Pascal X second Pa s (or Ns m−2). Mineral oils are typically0.02 to 0.05 Pa s at 40 degree C. 1 mPa s=1 Centipoise (cP) cP iscommonly used for absolute viscosity. The symbol for viscosity isusually u. When gravity is used to cause flow for the viscositymeasurement, the density p of the oil is involved and kinematicviscosity is reported=u/p. The basic SI unit is meter2/second (m2 s−1).Also 1 cm2 s−1=1 Stoke (St), and 1 mm2 s−1=1 centiStoke (cSt), cSt iscommonly used for kinematic viscosity. Viscosity (by ASTM D445) ofindustrial lubricants is commonly classified using the InternationalStandard Organization Viscosity Grade (ISOVG) system, which is theaverage viscosity in centiStokes (cSt) at 40 degree C. For example,ISOVG 32 is assigned to oils with viscosity between 28.8 and 35.2 cSt at40 degree C. Viscosity Index (VI) is a commonly used expression of anoil's change of viscosity with temperature. VI is based on twohypothetical oils with arbitrarily assigned Vi's of 0 and 100. Thehigher the viscosity index the smaller the relative change in viscositywith temperature. A less arbitrary indication of the change in viscositywith temperature is the viscosity temperature coefficient. For 40 to 100degree C. it is: Viscosity (cSt) at 40 degree C. minus Viscosity (cSt)at 100 degrees C=C−1, divided by the Viscosity (cSt) at 40 degrees C.Vapor pressure is the pressure exerted by a vapor on a liquid when it isin equilibrium with its own vapor. The higher the concentration of lowmolecular weight fractions, the greater the vapor pressure. Vaporpressure is reported as a pressure at a specified temperature.Volatility is reported as percent evaporative weight loss and ismeasured by ASTM method D-972. Flash point is an indication of thecombustibility of the vapors of a mineral oil, and is defined as thelowest temperature at which the vapor of an oil can be ignited underspecified conditions. Flash point is clearly related to safety. Hashpoint of lubricating oils is measured using ASTM D 92. An open cup ofoil is heated at a specific rate while periodically passing a smallflame over its surface. The flash point is considered to be the lowesttemperature at which the oil vapors will ignite, but not sustain aflame.

Surface tension is the surface energy between a liquid and its ownvapor, or air, or a metal surface. The word tension comes from the forcethat resists any attempt to increase the surface area. Surface tensionis thought to be a factor in the ability of an oil to “wet” a surface,in emulsion stability, and in the stability of dispersed solids.However, “wetting” has been found to be a complex phenomenon involvingoleophobic and oleophilic films on the metal surface. Some additives canmarkedly change surface tension. Paraffinic oils are straight chain orbranched aliphatic hydrocarbons belonging to the series with the generalformula C_(n)H_(2n)+2. Paraffin's are saturated with respect tohydrogen. A typical paraffinic oil molecule with 25 carbon and 52hydrogen atoms has a molecular weight of 352. Very high molecular weightparaffins are solid waxes, also dissolved in small amounts of mineraloils. Naphthenic or alicyclic oils have the characteristics ofnaphthenes, which are saturated hydrocarbons of which the moleculescontain at least one closed ring of carbon atoms. Paraffins arerelatively unreactive and thus have better oxidation stability comparedto naphthenes. In general, paraffins have a higher viscosity index thannaphthenic.

Physical and Chemical Properties of Mineral Oils that Affect Lubricationhave been dealt with by Douglas Godfrey of Herguth Laboratories, Inc.1995 which describes viscosity as being the property of a fluid thatcauses it to resist flow, which mechanically is the ratio of shearstress to shear rate. Viscosity may be visualized as a result ofphysical interaction of molecules when subjected to flow. Lubricatingoils have long chain hydrocarbon structures, and viscosity increaseswith chain length. Viscosity of an oil film, or a flowing column of oil,is dependent upon the strong absorption of the first layer adjacent tothe solid surfaces, and the shear of adjacent layers. Specific gravityis used which is ratio of the mass of a given volume to the mass of anequal volume of water. Therefore, specific gravity is dimensionless. Thespecific gravity of mineral oils also varies from 0.86 to 0.98 since thespecific gravity of water is 1 at 15.6 degree C. Specific gravitydecreases with increased temperature and decreases slightly as viscositydecreases for similar compositions. Reference 5 (pp. 482-484) gives thespecific gravity of 81 mineral oils at 15.6 degree C. Bulk modulusexpresses the resistance of a fluid to a decrease in volume due tocompression. A decrease in volume would increase density.Compressibility is the reciprocal of bulk modulus or the tendency to becompressed. Bulk modulus varies with pressure, temperature, molecularstructure and gas content. Generally, mineral oils are thought to beincompressible. In high pressure hydraulic systems a high bulk modulusor low compressibility is required to transmit power efficiently anddynamically. Bulk modulus is determined by measuring the volume of anoil at various pressures or derived from density measurements at variouspressures. Bulk modulus can also be measured by the speed of sound inoils under various pressures. A discussion of bulk modulus and valuesare given in References 9 and 10. Since a graph of pressure versusvolume gives a curve, the secant to the curve is used and is calledIsothermal Secant Bulk Modulus.

Gases are soluble in mineral oils to a limited amount. The amount varieswith the type of gas and oil temperature. For example, 8 to 9% of air,by volume, is soluble in mineral oil at room temperature and isinvisible. Dissolved gases affect oil viscosity, bulk modulus, heattransfer, oil and metal oxidation, boundary lubrication, foaming andcavitation. Boundary lubrication is improved by the oxygen in dissolvedair because it continuously repairs the protective oxide films onmetals. Dissolved oxygen is considered an important anti-scuffcomponent. The amount of dissolved gas become evident when gases comeout of solution vigorously when the oil is subjected to low pressures.The amount of soluble gas is measured by ASTM D 2780 “Solubility ofFixed Gases In Liquid Test”. This method physically separates the gasthrough an extraction process and measures the quantity volumetrically.This method allows for subsequent qualitative analysis of the extractedgas by any appropriate technique. If the amount of a gas in oil exceedssaturation, small bubbles will form, remain suspended, and the oil willappear hazy. This is called entrained gas. The bubbles slowly rise tothe surface. Bubbles of a gas, such as air, in an oil film cause holesthat reduce oil film continuity and decrease the film's ability toprevent solid-to-solid contact. The relative tendency of various oils torelease entrained gas is measured by a gas bubble separation method ASTMD 3427. The method uses a cylinder-like test vessel with gas inlet andoutlet ports. Air, or another gas (if of interest), is introduced intothe bottom of the vessel at a specified temperature and flow rate. Atthe end of seven minutes the gas flow is stopped and the change indensity as measured by a densitometer is recorded. The test is completewhen the total volume of entrained air is reduced to 0.20% by volume.The results are reported as the time it took for the oil to attain thisvalue.

Foaming is defined as the production and coalescence of gas bubbles on alubricant surface. Foam may be a result of a variety of problemsincluding air leaks, contamination, and over filling of sumps. Foamingcan cause loss of oil out of a vent and serious operational problems inmost lubricated systems. Excessive foam can starve bearings and pumps ofliquid lubricant (pump cavitation) causing failure, and cause poorperformance in hydraulic systems. The foaming characteristics of an oilare measured by ASTM D-892. Using a calibrated porous stone, air isblown into the bottom of a graduated cylinder for a specified time.Immediately upon completion of the blowing period, the foam that hasformed on the top of the oil is measured. Ten minutes after thecompletion of the blowing period, an additional measurement is made ofthe remaining foam as the foam retention characteristics of the oil. Theresults are reported in milliliters.

Examples of for use in the invention are many. Representativecommercially available plasticizing oils include Amoco® polybutenes,hydrogenated polybutenes, polybutenes with epoxide functionality at oneend of the polybutene polymer, liquid poly(ethylene/butylene), liquidhetero-telechelic polymers of poly(ethylene/butylene/styrene) withepoxidized polyisoprene and poly(ethylene/butylene) with epoxidizedpolyisoprene: Example of such polybutenes include: L-14 (320 Mn), L-50(420 Mn), L-100 (460 Mn), H-15 (560 Mn), H-25 (610 Mn), H-35 (660 Mn),H-50 (750 Mn), H-100 (920 Mn), H-300 (1290 Mn), L-14E (27-37 cst @ 100°F. Viscosity), H-300E (635-690 cst @ 210° F. Viscosity), Actipol E6 (365Mn), E16 (973 Mn), E23 (1433 Mn), Kraton L-1203, EKP-206, EKP-207,HPVM-2203 and the like. Example of various commercially oils include:ARCO Prime 55, 70, 90, 200, 350, 400; Tufflo oils 6006, 6016, 6016M,6026, 6036, 6056, 6206; Bayol, Bemol, American, Drakeol, Ervol, Gloria,Kaydol, Litetek, Lyondell Duroprime 55, 70, 90, 200, 350, 400; Ideal FG32, 46, 68, 100, 220, 460; Marcol, Parol, Peneteck, Primol, Protol,Sontex, Witco 40 oil, Ervol, Benol, Blandol, Semtol-100, Semtol 85,Semtol 70, Semtol 40, Orzol, Britol, Protol, Rudol, Carnation, Klearol;Witco oils 350, 100, 85, 70, 40, Pd-23, Pd-25, Pd-28, FG 32, 46, 68,100, 220, 460; Duroprime Ds-L, Ds-M, Duropac 70, 90, Crystex 22, Af-L,Af M, Ste Oil Co, Inc: Crystal Plus 70, 200, 350; Lyondell: DUROPRIME180, DUROPRIME 200, Duroprime DS L & M, Duropac 70, 90, Crystex 22,Crystex AF L & M; Chevron Texaco Corp: Superta White Oil 5, Superta 7,9, 10, 13, 18, 21, 31, 35, 38, 50; Penreco: Conosol 340, Conosol C-200,Drakeol 15, 13, 10, 10B, 9, 7, 5, 50; Peneteck; Ultra Chemical Inc,Ultraol White 60Nf, Ultraol White 50Nf; Witco Hydrobrite 100, 550, 1000,200PO, 280PO, 300PO, 380PO, 550PO, KLEAROL, CARNATION, SEMTOL 70,BLANDOL. SEMTOL 85, BERNOL, ERVOL, PROTOL, GLORIA, 250PO, 550 P0, LP100,LP150, LP200, LP350, 300PO, 380PO, SEMTOL 100, KAYDOL, LP200, LP250,LP300, LP350, Semtol 100, and the like.

Selected amounts of one or more compatible plasticizers can be used toachieve gel rigidities of from less than about 2 gram Bloom to about1,800 gram Bloom and higher. Tack may not completely be dependent uponthe amount of the glassy phase, by using selected amount of certain lowviscosity oil plasticizers, block copolymers of SEBS, SEEPS, SEPS, SEPn,SEBn, S-EB-EB/S-EB-S, and the like, gel tack can be reduced or the gelcan be made non-tacky.

As described at page 23 of copending applications U.S. Ser. No.09/285,809 and incorporated by reference above, minor amounts of one ormore compatible plasticizers can be utilized in forming the inventiongels. In providing non-tack gels, minor or major amount of plasticizersused can be low viscosity plasticizers having viscosities advantageouslyof not greater than typically about 30 cSt @ 40° C., for example 30, 29,28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11,10, 9, 8, 7, 6, 5, 4, and the like.

Major or minor amounts (based on 100 parts by weight of base elastomer)of any compatible second plasticizers can be utilized in forming theinvention gel, but because of the non-tack property of the inventiongel, the major amount of first plasticizers used can be low viscosityplasticizers having viscosities advantageously of not greater than about30 cSt @ 40° C., for example 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20,19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3 and thelike, specific examples include: 2.61, 3.9, 4.46, 4.56, 8, 12.76, 15.4,17.8, 19.5, 24.6, 29, 36.2, 37.5, 40.8, 40.9, 46.86, 48.5, 59.3, 60, 66,68.5, 72.8, 109.8, and lower values, in between and greater values asdetermined by ASTM D445.

Plasticizers in minor or major amount for use in the invention gels andinvention gel articles such as invention fishing bait gel articles whichrequire less tack, negligible tack, non-tack feel, and no tack, oilviscosities of about 10 and lower are of great advantage. Suchplasticizers typically exhibit about 10, 9, 8, 7, 6, 5, 4, 3, 2 cSt @40° C. and less; exhibit an initial ASTM D2827 distillation boilingpoint (IBP) below about 490° F. ranging from about 480° F. to about lessthan 300° F., including 290° F., 310° F., 320° F., 330° F., 340° F.,350° F., 360° F., 370° F., 375° F., 385° F., 395° F., 405° F., 416° F.,420° F., 435° F., 438° F., 450° F., 455° F., 460° F., 477° F., 485° F.,and the like. In certain cases a plasticizer can exhibit a highviscosity of 17.8 while maintaining a low IBP of 477° F.

The invention gel tack decreases with decreasing oil viscosities of fromabout 30 to 3. The invention gels' self-adhesion also decreases withdecreasing oil viscosities. Invention gels which are non-tacky to thetouch can be achieved using oils with viscosities of about 10 cSt @ 40°C. and less. Best result can be achieved using oils with viscosities ofabout 6 and less. Oils of higher viscosities of from about 500 cSt @ 40°C. to about 30 produce higher and higher tack with increase inviscosities. Heat temperature set resistance improves with increase inoil viscosity. Oils with viscosities less than about 15 exhibit heat setat about 50° C. Therefore a combination of low viscosity oils to improvelow tack and high viscosity oils to improve set can be achieved byblending various oils having the desired viscosities for the desired enduse. The disassociation of polystyrene is about 100° C. to about 135°C., the invention gels do not melt below the disassociation temperatureof polystyrene. It is important that fishing bait when stored in afishing box in the hot Sun at about 50° C. to about 58° C. do not suffersubstantial heat set as tested at these temperatures in a 108′ U bendfor one hour.

It has been found that the lower the oil viscosity, the lower the heatset of the resulting gel composition and the higher the oil viscosityuse in the gel compositions of the invention, the higher the heat set ofthe resulting gel composition. For example, if the first plasticizer isless than about 50 SUS @ 100° F., the heat set of the resulting gelcomposition comprising 100 parts of copolymers of equal parts of SEEPS4055 and Kraton G 1651 with about 600 parts by weight of the firstplasticizer, the resulting is found to have a heat set less than that ofa conventional PVC plastisol fishing bait at about 50° C. However, asthe 50 Vis SUS @ 100° F. oil of the formulation is gradually replacedwith a higher viscosity oil of about 80-90 SUS @ 100° C., the heat setdeformation improves with increasing amounts of the higher viscosityoil. In order to obtain equal heat set performance as conventional PVCplastisol fishing bait, the first and second plasticizers would have tobe of equal amounts in the gel composition. Replacing the firstplasticizer with a greater amount would increase the gel tack. If tackis not of great concern, then a higher amount of the second plasticizerswould be beneficial for improving heat set at higher and highertemperatures to the point that the second plasticizers can reach greaterthan 2525 SUS @ 100° C. (Ideal FG 100, 220, or 460 oil) the resultinggel composition would not exhibit set at even temperatures greater than400° F.

The cited first plasticizers with or without one or more secondplasticizers can be used in sufficient amounts to achieve a gel rigidityof from about 20 gram Bloom to about 1,800 gram Bloom. The secondplasticizers in effective amounts in combination with the firstplasticizers can provide a greater temperature compression set than agelatinous composition having the same rigidity formed from the firstplasticizers alone. The second plasticizers when used can provide agreater temperature compression set than a gelatinous composition havingthe same rigidity formed from the first plasticizers alone or formedfrom a combination of the first plasticizers and the secondplasticizers. The first plasticizers being in effective amounts withsaid second plasticizers can provide a Gram Tack lower than a gelatinouscomposition having the same rigidity formed from the second plasticizersalone.

Generally, various low to high viscosity commercially availableplasticizing oils with average molecular weights ranging from less thanabout 200 to greater than about 700 may also be used (e.g. H-300 (1290Mn)), specific examples involved: 220, 229, 234, 245, 299, 328, 343,348, 312, 375, 343, 404, 360, 414, 409, 424, 377, 490, 390, 396, 424,517, 546, and values lower, in between and greater as determined by ASTM2502. It is well know that minor and sufficient amounts of Vitamin E isadded to the described commercially available oils during bulkprocessing which is useful as a oil stabilizer, antioxidant, andpreservative.

Of all the factors, the amount and varying viscosities of plasticizingoils can be controlled and adjusted advantageously to obtainsubstantially higher tear and tensile strength gels, low compressionset. Another embodiment which is of advantage for improving hightemperature heat set of the gel articles is to utilize silicon dioxidepowder in combination with one or more low viscosity plasticizing oils.The combination can form gels exhibiting lower compression set and lowerdistortion under load under high heat conditions such as in a fishtackle box under the Summer sun. The amount of silicon dioxide can rangefrom less than less than about 0.5% to about 7% by weight of oil andhigher. Examples of useful amounts of silicon dioxide include: 1%, 2%,3%, 4%, 5%, 6%, 7%, and lower, in between, and higher values. In termsof 50/50 volume of silicon dioxide powder to oil, less than 0.5%, 1%,1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and greater weight of MSCabo-sil® (silica powder, a form of silicon dioxide) (including minor %amounts in-between) for example is approximately equal to 50% volume lowviscosity of Witco 40 oil. By using low viscosity plasticizers withsilica powder, less amounts of higher viscosity plasticizers is neededto achieve lower compression set at increasing temperature conditions.

The improvements in tensile strength of the invention gels areaccompanied by corresponding increase in gel rigidity as the amount ofplasticizing oils can be lowered until the rigidity of the inventiongels becomes much higher than that of the rigidity of the gums (forexample) which surround the teeth. Although higher tensile strengths canbe obtained as the amount of plasticizing oils in the gel approacheszero, when use as a floss, the tensile strength, however, can bemaintained at an acceptable gel rigidity (at sufficient highplasticizing oil levels) to be as soft as the gums for flossing. Forexample, the rigidities of a gel containing 100, 200, or 300 parts byweight of oil is much higher than a gel containing 300, 400, 500, 600,800, or 900 parts of oil. Selected amounts of one or more low viscosityplasticizers can be use to advantage in forming the gels of theinvention having little or no tack.

The refractive index of commercially available oils at 77° F. cantypically vary from below about 1.440 to above about 1.495 including1.442, 1.446, 1.4485, 1.45, 1.4578, 1.4596, 1.461, 1.4622, 1.4625,1.464, 1.4651, 1.4652, 1.4658, 1.4673, 1.4697, 1.4697, 1.47, 1.471,1.4731, 1.4736, 1.4741, 1.4746, 1.4752, 1.4755, 1.4755, 1.4755, 1.4763,1.4764, 1.4765, 1.4786, 1.479, 1.4797, 1.4805, 1.4809, 1.4838, 1.4919,and the like, typical examples include: 1.4438, 1.4462, 1.457, 1.4485,1.4578, 1.4625, 1.4822, 1.4651, 1.4652, 1.4673, 1.4674, 1.4755, 1.4697,1.4755, 1.4731, 1.4786, 1.4719, 1.4736, 1.4746, 1.4797, 1.4755, 1.4805,1.4809, 1.4765, 1.4763, 1.4752, and values lower, in-between and greateras determined by ASTM D1218.

Not only can the invention gels be made translucent, opaque, non-tackyto the touch or extremely tacky, the gels are naturally transparent andoptically clear suitable for optical use within a wide range of desireindex of refractions. The gels can be made strong, elastic, highly tearresistant and rupture resistant. The invention gels can be formed intoany shape for the intended use such as solid shapes for use as articlesof manufacture, thin and thick sheets, strands, strings, ropes, fibers,fine silk like filaments can be applied in its molten state onto varioussubstrates to formed composites and blended with various substances toform composite blends.

This physical elastomeric network structure of the invention gels arereversible, and heating the polymer above the softening point of theglassy domains temporarily disrupt the structure, which can be restoredby lowering the temperature. During mixing and heating in the presenceof compatible plasticizers, the glassy domains (A) unlock due to bothheating and solvation and the molecules are free to move when shear isapplied. The disruption and ordering of the glassy domains can be viewedas a unlocking and locking of the elastomeric network structure. Atequilibrium, the domain structure or morphology as a function of the (A)and (B) phases (mesophases) can take the form of spheres, cylinders,lamellae, or bicontinous structures. The scale of separation of thephases are typically of the order of hundreds of angstroms, dependingupon molecular weights (i.e. Radii of gyration) of theminority-component segments. The sub-micron glassy domains whichprovides the physical interlocking are too small to see with the humaneye, too small to see using the highest power optical microscope andonly adequately enough to see using the electron microscope. At suchsmall domain scales, when the gel is in the molten state while heatedand brought into contact to be formed with any substrate and allowed tocool, the glassy domains of the gel become interlocked with the surfaceof the substrate. At sufficiently high enough temperatures, with orwithout the aid of other glassy resins (such as polystyrene homopolymersand the like), the glassy domains of the copolymers forming theinvention gels fusses and interlocks with even a visibly smoothsubstrate surface such as glass. The disruption of the sub-microndomains due to heating above the softening point forces the glassydomains to open up, unlocking the network structure and flow. Uponcooling below the softening point the glassy polymers reforms togetherinto sub-micron domains, locking into a network structure once again,resisting flow. It is this unlocking and locking of the networkstructure on the sub-micron scale with the surfaces of various materialswhich allows the gel to form interlocking composites with othermaterials.

A useful analogy is to consider the melting and freezing of a watersaturated substrate, for example, foam, cloth, fabric, paper, fibers,plastic, concrete, and the like. When the water is frozen, the ice is toa great extent interlocked with the substrate and upon heating the wateris able to flow. Furthermore, the interlocking of the ice with thevarious substrates on close examination involves interconnecting ice in,around, and about the substrates thereby interlocking the ice with thesubstrates. A further analogy, but still useful is a plant or weed wellestablished in soil, the fine roots of the plant spreads out andinterconnects and forms a physical interlocking of the soil with theplant roots which in many instances is not possible to pull out theplant or weed from the ground without removing the surrounding soilalso.

Likewise, because the glassy domains are typically about 200 Angstromsin diameter, the physical interlocking involve domains small enough tofit into and lock with the smallest surface irregularities, as well as,flow into and flow through the smallest size openings of a poroussubstrate. Once the gel comes into contacts with the surfaceirregularities or penetrates the substrate and solidifies, it becomesdifficult or impossible to separate it from the substrate because of thephysical interlocking. When pulling the gel off a substrate, most oftenthe physically interlocked gel remains on the substrate. Even a surfacewhich may appear perfectly smooth to the eye, it is often not the case.Examination by microscopy, especially electron microscopy, will showserious irregularities. Such irregularities can be the source ofphysical interlocking with the gel.

Regarding resistance to fatigue, fatigue (as used herein) is the decayof mechanical properties after repeated application of stress andstrain. Fatigue tests give information about the ability of a materialto resist the development of cracks or crazes resulting from a largenumber of deformation cycles. Fatigue test can be conducted bysubjecting samples of amorphous and gels to deformation cycles tofailure (appearance of cracks, crazes, rips or tears in the gels).

Tensile strength can be determined by extending a selected gel sample tobreak as measured at 180° U bend around a 5.0 mm mandrel attached to aspring scale. Likewise, tear strength of a notched sample can bedetermined by propagating a tear as measured at 180° U bend around a 5.0mm diameter mandrel attached to a spring scale.

When the copolymers are combined with oils of selected refractive index,the refractive index of the resulting gel can exhibit a correspondingrefractive index greater than the oil(s) alone. This depends on theamount and type of copolymer(s) used. By selecting the refractive indexand ratio of the oil(s) and selecting one or more of the copolymers ofthe invention gel, the final refractive index of the gel can be match toalmost any degree require for end use gel article. Moreover, a matchingof two different refractive index gels or gel pairs (one greater densityand one lower density), light can be channeled within the gel having thehigher refractive index (greater density). In this way, light can bedissipated or allowed to escape from the higher refractive index gel(greater density) to a lesser extent. By forming adjacent lowerrefractive index gel layers on all sides of a higher refractive indexgel shaped article such as a sheet, rod, tube, and the like, light beingtransmitted in the higher refractive index gel can experience less lightloss. Generally, when light passes from a gel of another of differentdensity in a direction normal to the interface between the two gels, itsdirection is unaltered. If, however, it makes an angle different fromzero with the normal, it is refracted, in the sense of being bent towardthe normal in the gel of greater density. In passing in the oppositedirection it is bent away from the normal in the gel of lesser density.The quantitative law of refraction is the well known Snell's Law. Gelsof various forms and of various indices of refraction can be made toemploy the principle of total reflection. Light incident on the gel-gelinterface at an angle greater than the critical angel have no possiblepath in the lower density gel and are therefore totally reflected. FromSnell's Law, if the angle of incidence, i, is such that the refractedand reflected light are at right angles to each other, then for a gel ofrefractive index n equals tan i. This relationship is known as Brewster'law, which states that the angle of incidence for complete polarizationis that angle whose tangent is equal to the index of refraction of thereflecting gel material. The index n of the gel articles of theinvention can range from less than about 1.400 to greater than aboutthat of 1.500. The gels of the invention are excellent for claddingglass for purpose of transmitting light in glass. This is because thegel cladding in most instances can be formulated to a refractive indexlower than glass.

In general, the basis of this invention resides in the fact that one ormore of a high viscosity linear multiblock and star-shaped multiblockcopolymers or a mixture of two or more of such copolymers having (A) endblock to elastomeric block ratio preferably within the contemplatedrange of styrene to rubber ratios of from about 20:80 to about 40:60 andhigher, more preferably from between about 31:69 to about 40:60 andhigher when blended in the melt with one or more of an appropriateamount of plasticizing oil makes possible the attainment of inventiongels having a desirable combination of physical, mechanical, andtribological properties, notably high elongation at break of at least1,600%, ultimate tensile strength of about 8×105 dyne/cm2 and higher,low elongation set at break of substantially not greater than about 2%,tear resistance of 5×10⁵ dyne/cm² and higher, substantially about 100%snap back when extended to 1,200% elongation, an adhesive tack, a lowtack, a no tack surface.

More specifically, the invention gels of the present invention exhibitone or more of the following properties. These are: (1) tensile strengthof about 8×105 dyne/cm2 to about 107 dyne/cm2 and greater; (2)elongation of less than about 1,600% to about 3,000% and higher; (3)elasticity modulus of about 104 dyne/cm2 to about 106 dyne/cm2 andgreater; (4) shear modulus of about 104 dyne/cm2 to about 106 dyne/cm2and greater as measured with a 1, 2, and 3 kilogram load at 23° C.; (5)gel rigidity of about less than about 2 gram Bloom to about 1,800 gramBloom and higher; (6) tear propagation resistance of at least about5×10⁵ dyne/cm²; (7) and substantially 100% snap back recovery whenextended at a crosshead separation speed of 25 cm/minute to 1,200% at23° C. Properties (1), (2), (3), and (6) above are measured at acrosshead separation speed of 25 cm/minute at 23° C.

As the invention gels formed from multiblock copolymers having more andmore midblock polymer chains can be expected to exhibit greater delayrecovery form extension or longer relaxation times with increasingnumber of midblocks and increasing midblock lengths, such invention gelshaving more than three midbtocks forming the copolymers can exhibitextreme tear resistance and excellent tensile strength while at the sametime exhibit almost liquid like properties. For example, a fun toy canbe made from (S-E-EB-E-S), (S-B-EB-EB-S), (S-E-EP-E-EP-S),(S-P-EB-P-EB-S), (S-E-EB-E-EB-E-S), (S-E-EP-E-EP-E-EP-E-S),(S-E-EP-EP)_(n), (S-B-EP-E-EP)n, (S-E-EP-E-EP-E)_(n),(S-E-EB-E-EB-E-EB-E-EB-S)_(n) copolymer invention gels which are moldedinto cube shapes when placed on the surface of a incline will collect itself together and flow down the incline as a moving body much like avolume of water moving on a high surface tension surface. This is due tothe greater distance between the end block (A) domains. Such liquid likeperforming invention gels can be very strong and exhibit extreme tearresistance as exhibited by invention gels made from (S-E-EP-S)multiblock copolymer invention gels with shorter (A) distance betweendomains. Such liquid like invention gels when shaped into a cube will bedeformed by the force of gravity on Earth, but will retain its memoryand regain to its molded cube shape when released in outer space orreform into a cube if let loose in a container of liquid of equaldensity. As a comparison, such a toy formed in the shape of a large cubefrom a high viscosity triblock copolymer with a plasticizer content of1:1,600 parts will be flattened by the force of gravity and run down anincline, but is very fragile and will start to tear if attempt is madeto pick it up by hand. This is an excellent comparison of the differenceof tear resistance difference between triblock copolymer gels andmultiblock copolymer invention gels. A useful application is to use suchan elastic liquid gel volume to fill a container or to encapsulate anelectrical or electronic component in a container filling everyavailable space, when needed, the shapeless gel volume can be removed bypouring it out of the container whole.

The shear resistant characteristics of the invention gels can beindirectly determined by subjecting the gel to the shear forces of apair of twisting strings and the resulting inward pulling forces of thetwisting strings can be directly read off of a spring scale. As a pairof strings are gradually twisted, typical values will range from lessthan one pound to fifty pounds and greater. As the string is beingtwisted (simulating increased shearing forces), the measured pullingforces can range from a low value of 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28,29, 30, 31 . . . to values of 40, 50, 60, 70, 80 pounds and greater.

Gel material of low strength can not resist the tremendous shearingaction of the twisting strings. The twisting action of the strings canexhibit a first order twist, a second order twist, or higher ordertwists. A first order twist refers to one or more twists of a pair ofstrings (i.e. a pair of strings when twisted together forms a small,tight binding helix). A second order twist refers to one or more largebinding helixes build up by a pair of strings that have been twistedbeyond the maximum number of twist which normally produce small tightbinding helixes of the first order kind. Similarly, a third order twistrefers to a much larger tightly binding helix build up by the maximumnumber of second order twists produced by the pair of twisting strings.The third order twist may be manifested by the appearance of a branch oftwo or more twist of the first order twisting strings.

The order of twisting will increase (from a one, two, three, and higherorder twist) until the rubber band breaks. Likewise, a looped stringwith one end attached to a spring scale and the other end attached to afixed anchor can be twisted into a first, second, third, and higherordered twist state. This method can be utilized to directly measure theforce generated for each ordered twist states. The static forcegenerated by twisting a string on a spring scale is a way of determiningthe shear force generated in the shearing action of forcing the gelfloss between two closely contacting teeth when flossing.

In considering dental flossing criteria, one or more of the followingconditions can be regarded as useful factors for dental flossing gels.

SHEAR RESISTANT CRITERIA: for the invention gels to be considered usefulfor flossing, the invention gels, critically, can withstand a twistingstring shearing force of at least about 5 Kg, more advantageously atleast about 8 Kg, and still more advantageously at least about 10 Kg ofinward pulling force of a pair of twisting strings measured directly ona spring scale.

FLOSSING CYCLE CRITERIA: for the invention gels to be considered usefulfor flossing, the invention gels, critically, can advantageously be ableto perform at least 4 flossing cycles, more advantageously 8 cycles, andstill more advantageously of about 20 cycles without breaking apart whena 3.0 mm diameter gel strand is tested on a set of simulated upper frontteeth fully contacting under a uniform spring load of (0.9027 Kg) twopounds. The simulated upper front teeth comprises two small stainlesssteel rollers (⅜″ dia) facing lengthwise parallel and forced together soas to form a contact length of ½ inches under a spring load of twopounds as measured by a Entran® model ELO-200-4 load cell adjusted by astraight micrometer at room temperature.

GEL STRENGTH CRITERIA: for the invention gels to be considered usefulfor flossing, the invention gels, critically, can advantageously exhibita tensile strength of at least 5 Kg/cm2 (when extended to break asmeasured at 180o U bend around a 5.0 mm mandrel attached to a springscale) and more advantageously at least 8 Kg/cm2, and still moreadvantageously of about 10 Kg/cm2 and higher. The invention gels usefulas dental floss can exhibit tensile strengths at break of at least 20Kg/cm2, more advantageously of at least 40 Kg/cm2, and exceptionallymore advantageously at least 60 Kg/cm2. Typically, the tensile strengthsrange from about 20 Kg/cm2 to about 110 Kg/cm2 and higher, moretypically from about 30 Kg/cm2 to 80 Kg/cm2 and higher, especially moretypically from about 40 Kg/cm2 to about 90 Kg/cm2 and higher, andexceptionally typically from about 50 Kg/cm2 to about 100 Kg/cm2 andhigher.

PROPAGATING TEAR CRITERIA: as a minimum, for the Invention gels to beconsidered useful for flossing, the invention gels, critically, canadvantageously exhibit a propagating tear force (when propagating a tearas measured at 180 o U bend around a 5.0 mm diameter mandrel attached toa spring scale) of at least about 1 Kg/cm, more advantageously at least2 Kg/cm, and still more advantageously of about 3 Kg/cm and higher. Theinvention gels useful as dental floss can exhibit tear strengths of atleast 4 Kg/cm and higher, more advantageously of at least 6 Kg/cm andhigher, exceptionally more advantageously of at least 8 Kg/cm andhigher. Typically, the tear propagation strength can range from about 5Kg/cm to about 20 Kg/cm and higher, more typically from about less than5 Kg/cm to about 25 Kg/cm and higher, especially more typically formabout less than 6 Kg/cm to about 30 Kg/cm and higher, and exceptionallymore typically from about less than 8 Kg/cm to about 35 Kg/cm andhigher. For the Invention gels to be considered useful for flossing, theinvention gels, critically, can advantageously exhibit a propagatingtension tear force (when a cylindrical sample is notched and a tear isinitiated at the notched area and propagated past its maximumcylindrical diameter by length-wise stretching of the cylindricalsample) of at least about 1 Kg/cm, more advantageously at least 2 Kg/cm,and still more advantageously of about 4 Kg/cm and higher. The extremetear resistant invention gels typically will exhibit even higher tensiontear values.

RIGIDITY CRITERIA: the rigidities of the extreme tear resistant usefulfor flossing can advantageously range from about 350 gram to about 1,800gram Bloom, more advantageously from about 400 gram to about 1,500 gramBloom, especially more advantageously from about 450 gram to about 1,200gram Bloom, still more advantageously from about 450 gram to about 1,000gram Bloom, and less advantageously at values of greater than 1,800 gramBloom.

In general, as a minimum, the flossing invention gels can exhibitseveral critical properties, including advantageously the ability to:(1) withstand a shearing force of at least about 5 Kg under the stringtwisting test described above, (2) perform at least 4 flossing cycleswithout breaking apart when tested on a set of simulated upper frontteeth fully contacting under a uniform spring load of two pound, (3)exhibit a tensile strength of at least 5 Kg/cm2 and higher, (4) exhibita propagating tear force at 180 o U bend tear test of at least about 1Kg/cm, and (5) exhibit a propagating tension tear force (on a notchedcylindrical sample) of at least about 1 Kg/cm.

For use as a dental floss, the gel is made (by extruding, spinning,casting, etc) as a continuous gel strand, the gel strand can be in theshape of a fiber of a selected diameter (from less than about 0.15 toabout 5.0 mm and greater) as a continuous tape having a selected widthand thickness (less than 0.10 mm thin to about 5.0 mm and thicker) or inany desired shape suitable for flossing. The fiber, tape or a selectedshape is then cut to a desired length, rolled up and placed into adispenser suitable for containing and dispensing a measured use amountof gel floss. The continuous fiber and tape can be partly cut or notchedfor measured single or multiple use. When the floss is pulled from thedispenser to a point showing the notched or cut mark on the length ofgel floss, the lid is pushed down on the gel floss nipping it andallowing the floss to be further pulled and separated at the notched orcut point. Additionally, a suitable floss dispenser containing ameasured length of gel floss can be fitted with a cutting edge attachedto its lid or on its body and the uncut and un-notched gel floss can bedispensed from the dispensing container and cut at the desired measureduse length by pressing close the dispenser cutting edge down on thefloss so as to nip and cut the gel or by simply closing the dispenserlid or running the gel along the cutting edge on the dispenser bodyseparating a useful length of gel floss.

One of the difficulty of providing a standard length of invention gelfloss strand is that one user may require a longer comfortable lengthwhile another user may need only a shorter length. Further a child orthe elderly would have additional difficulties in using a gel strand,because of the requirement of wrapping it around the fingers or hand.Therefore, an invention gel article specifically designed for flossingas shown in FIGS. 5 a-5 m would be ideal. The invention floss gelarticles provides a selected fix dose in terms of of area, width, andlength for flossing. It provides for secure holding without the need forwrapping. It can be packaged more simply instead of the need to insert acoiled, a twisted, a tangled strand into a container. The containeruseful for holding the new invention floss gel articles can comprise asee through flexible film package or see through plastic container. Theinvention gel floss articles is a shaped invention gel formed into ashaped article tube and illustratively use in FIGS. 5 a-5 m. FIG. 5 ashows a lengthwise crossection of the invention gel floss tube. FIG. 5 bshows a lengthwise cross-section of tube elements at both ends with aflat gel middle. FIG. 5 c shows a flatten 5 b view from one edge of theflatten gel floss. FIG. 5 d shows two curved inner terminus of the tubesnext to the flat width gel flossing area. FIG. 5 e shows a moreconforming version of the invention gel floss with the flossing widtharea view from one edge. FIGS. 5 f and 5 j shows two thumbs and twofingers inserted into 5 e respectively. FIG. 5 g shows a deformedelongated gel floss tube. FIGS. 5 h and 5 i shows gel floss tubes 5 a ofdifferent tube diameters. FIGS. 5 k-5 m shows gel floss tubes beingfurther and further extended for use. The ends of the tubes of theinvention gel floss articles can be rolled onto and off the thumbs andfingers for easy of use. The invention gel floss tubes can be donned onadjacent finger digits or opposing finger digits. The tube at each endlength can have different diameters for insertion to accommodatedifferent size digits. Once rolled onto the digits and pulled, the tubeend length diameters can gradually reduce in size and becomes tighterfitting and grips the digits more firmly preventing the ends fromslipping off the digits. The tube area or width portion for insertion inthe tooth gap is adjusted for varying thickness by stretching the donneddigits apart forcing the tube to collapses and become thinner andthinner suitable for flossing. No matter what the gap space between thetooth, the invention gel floss articles can accommodate because of thevariable thickness of the flossing area or width can be controlled bythe extension of the digits. The tube portion surrounding the digits canbe quickly and easily rolled off after use. Such invention floss gelarticles do not have the problems inherent of gel stands.

In practice, typically during flossing, a gel strand will under govarious deformations, some of these deformations can be measured,including original shape, extended shape under tension, nipping force,and nipped deformation under a measured force and width. Typically, anyshaped gel strand can be used for flossing, a square cross-section, acircular cross-section, a rectangular cross-section, round, oval, etc.For example, a 2.35 mm diameter strand when extended under a force of2.5 kg can be nipped down to 0.14 mm thickness (along a 3 mm uniformwidth of its cross-section) by a force of 0.9072 Kg (2.0 pound force), areduction of 16.78: 1; a 1.89 mm diameter strand when extended under aforce of 2.5 kg can be nipped down to 0.14 mm thickness by a force of0.9072 Kg (2.0 pound force), a reduction of 13.5: 1; a 2.75 mm diameterstrand when extended under a force of 2.5 kg can be nipped down to 0.19mm thickness by a force of 0.9072 Kg (2.0 pound force), a reduction of14.4:1; and a 2.63 mm diameter strand when extended under a force of 2.5kg can be nipped down to 0.19 mm thickness by a force of 0.9072 Kg (2.0pound force), a reduction of 13.8:1. the cross-section of the gel flosscan be reduced to any degree by stretching and nipping (from less thanabout 1% to about 1,600% and higher). Advantageously, a gel having therequired strength, tear resistance, gel rigidity, and othercharacteristics described can be formed into a floss of any selectedcross-section and thickness provided the floss is capable of beingstretched when flossing under tension without breaking. Typically thestretching or pulling force is from about less than 0.1 Kg to about 3 Kgand higher. The cross-section of the strand of gel floss can be capableof being nipped by a 0.9027 Kg (2 pounds) force applied across a widthof 3 mm from its original cross-sectional dimensions to a nippedthickness of about 3.0 mm to about 0.02 mm and lower, moreadvantageously from about 2.5 mm to about 0.04 mm and lower, still moreadvantageously from about 2.0 mm to about 0.08 mm and lower; especiallyadvantageously from about 1.5 mm to about 0.15 mm and lower; especiallymore advantageously from about 1.2 mm to about 0.20 mm and lower;especially still more advantageously from about 1.0 mm to about 0.25 mmand lower.

The invention gels made from higher viscosity copolymers are resistantto breaking when sheared than triblock copolymer gels. This can bedemonstrated by forming a very soft gel, for example 100 parts copolymerto 800 parts plasticizing oil. The soft gel is cut into a strip of 2.5cm × 2.5 cm cross-section, the gel strip is gripped lengthwise tightlyin the left hand about its cross-section and an exposed part of the gelstrip being gripped lengthwise around its cross-section tightly by theright hand as close to the left hand as possible without stretching.With the two hands gripping the gel strip's cross-section, the hands aremoved in opposite directions to shear apart the gel strip at itscross-section. The shearing action by the gripping hands is done at thefastest speed possible as can be performed by human hands. The shearingaction is performed at a fraction of a second, possible at about 0.5seconds. Using this demonstration, the copolymer invention gels will noteasily break completely apart as would gels formed from triblockcopolymers. In some cases, it will take two, three, or more attempts toshear a high viscosity copolymer gel strip this way. Whereas, a lowerviscosity triblock copolymer gel strip can be sheared apart on the firsttry. For gels made from copolymers with viscosities of 5 wt % solutionin Toluene, their shear resistance will decrease with decreasingviscosity. For example, the shear strengths as tested by hand shearingdescribed above of invention gels made from copolymers having polymerviscosities of 150, 120, 110, 105, 95, 90, 89, 85, 70, 60, 58, 48, 42,40, 35, 28, 27, 25, 21 cps, and the like can be expected to decreasewith decreasing viscosity.

The tensile strengths of multiblock copolymer invention gels made fromhigher viscosity copolymers can be slightly lower than or equal to thetensile strengths of gels made from lower solution viscosity triblockcopolymers. Strands of invention gels comprising higher viscositymultiblock copolymers will perform better than gel strands made fromgels of lower viscosity triblock copolymers when used in flossingamalgam molars and more than three times better when used in flossingfront teeth.

Invention gels, in general, will exhibit higher tensile and greater tearresistance than their parent invention gels containing higherconcentrations of plasticizer. As compared to spongy nylon, regularwaxed nylon, and extra fine unwaxed nylon when flossing amalgam molars,the performance of multiblock copolymer invention gels are on theaverage substantially better.

Another embodiment of the invention gels is making adherent inventiongels by selecting high and higher viscosity plasticizers and decreasingselected low and lower viscosity plasticizers in formulating theinvention gels, invention gel articles, invention (polymer blend) gelcomposites and articles, and invention gel composites. The choice ofhigh and higher viscosity plasticizers allows for increase in tack oradhesives gel properties without other additives. By eliminating low andlower viscosity plasticizers, tack is increased; by eliminating all lowand lower viscosity plasticizers, higher and higher tack is achieved, ashigher viscosity plasticizers are use, higher tack is achieved.Likewise, selected amounts of higher viscosity plasticizers can decreasegel compression set and distortion set at higher and highertemperatures. For example invention gel made from a plasticizer having aviscosity of about 70 cSt @ 40° C. can exhibit lower compression heatset and higher adhesion or high tack than a gel made from a plasticizerwith a viscosity of about 36 cSL An invention gel made from aplasticizer having a viscosity of about 70 cSt @ 40° C. can exhibitlower compression heat set and higher adhesion or high tack than a gelmade from a plasticizer with a viscosity of about 36 cSt. An inventiongel made from a plasticizer having a viscosity of about 100 cSt @ 40° C.can exhibit lower compression heat set and higher adhesion or high tackthan a gel made from a plasticizer with a viscosity of about 70 cSt. Aninvention gel made from a plasticizer having a viscosity of about 66 cSt@ 40° C. can exhibit lower compression heat set and higher adhesion orhigh tack than a gel made from a plasticizer with a viscosity of about46 cSt. An invention gel made from a plasticizer having a viscosity ofabout 18 cSt @ 40° C. can exhibit lower compression heat set and higheradhesion or high tack than a gel made from a plasticizer with aviscosity of about 10 cSt An invention gel made from a plasticizerhaving a viscosity of about 8 cSt @ 40° C. can exhibit lower compressionheat set and higher adhesion or high tack than a gel made from aplasticizer with a viscosity of about 5 cSt An invention gel made from aplasticizer having a viscosity of about 4.5 cSt @ 40° C. can exhibitlower compression heat set and higher adhesion or high tack than a gelmade from a plasticizer with a viscosity of about 2.5 cSL

A further embodiment of the invention adherent gels is the incorporationof minor amounts of SEP, SEB, SEBSEB and SEPSEP block copolymers forimproving the tack of the SEEPS and CD SEB-EB/SEBS, CD SEBS, CD SEPS, CDSEEPS, and CD SEP-EP/SEPS block copolymers invention gels.

In formulating the adherent invention gels, higher and higher initialboiling point (IBP) plasticizers produce more and more adhesiveness inthe gels of the invention. In theory, the formulation of adherent andnon-adherent gels, their tack and non-tack property balance can be dueto the viscosity and IBP of the plasticizers used. An example is Witcooil Benol having an IBP of about 475° F. and a viscosity of about 18 cSt@ 40° C. This being contrary to the reasoning that lower and lowerviscosity plasticizers produce decreases in tack An invention gel madefrom Witco Carnation® having IBP of about 525 and viscosity of about 13cSt can exhibit a higher tack than made with Benol® which viscosity isabout 5 cSt higher. Likewise, Witco Protol® with a viscosity of about 36cSt has a higher viscosity than abut 25 cSt for Witco Ervolg), but canexhibit lower tack. Likewise for Witco Bandol® with a cSt of about 16can exhibit a lower tack than Carnation® with a viscosity of 13 cStThese anomalies can be explained when a comparison is made of the IBP ofProtol®, Benol®, and Blandol®; their IBP are lower than other oils withlower viscosities. This can only be if these oils are not “straightcuts” from the distillation process, but a blend of different viscosityoils containing a small or very small amounts of lower viscosity oils orlower average molecular weight oils. It is because of the small or verysmall amount of lower viscosity oils which suppress their IBP thatinvention gels made from these lower IBP, but higher over all viscosityoils are less tacky. This surprise, instead, confirms the theory thatlower and lower viscosity or lower and lower average molecular weightcomponents of any given batch or grade of plasticizer with lower IBPimpart less tack to the invention gels and invention gel articles. Inother words, the amount of or higher viscosity of or higher IBP of theplasticizers do not matter as much as the presence of small amounts oflower viscosity or lower IBP plasticizers to impart lower tack in theinvention gels and invention gel articles. The theory is furthersupported by comparing the specific Gravity @ 25° C. of various gradesto IBP of the plasticizers.

Therefore this fair warning. When considering plasticizers to formulateadherent invention gels and non-adherent invention gels, the viscosityof the plasticizers can not be solely relied upon. When consideringplasticizers to formulate improved compression heat set invention gels,the IBP of the plasticizers can not be solely relied upon. Whenconsidering plasticizers to formulate adherent invention gels,non-adherent invention gels, and compression heat set, the viscosity ofthe plasticizers can not be solely relied upon. When consideringplasticizers to formulate compression heat set invention gels, theviscosity of the plasticizers can not be solely relied upon.

A still further embodiment of the invention gels is making adherentinvention gels by the incorporation of adhesion resins is to providestrong and dimensional stable adherent invention gels, invention gelcomposites, and invention gel articles. Typically such adherentinvention gels can be characterized as adhesive invention gels, softadhesives or adhesive sealants. Strong and tear resistant adherentinvention gels may be formed with various combinations of substrates oradhere (attach, cling, fasten, hold, stick) to substrates to formadherent gel/substrate articles and composites, including gel to gelcomposites.

Various glassy phase associating resins having softening points aboveabout 120° C. can also serve as additives to increase the glassy phaseof the Invention gel and met the non-tackiness criteria, these include:Hydrogenated aromatic resins (Regalrez 1126, 1128, 1139, 3102, 5095, and6108), hydrogenated mixed aromatic resins (Regalite R125), and otheraromatic resin (Picco 5130, 5140, 9140, Cumar LX509, Cumar 130, Lx-1035)and the like.

The commercial resins which can aid in adhesion to materials (plastics,glass, and metals) may be added in minor amounts to the invention gels,these resins include: polymerized mixed olefins (Super Sta-tac,Betaprene Nevtac, Escorez, Hercotac, Wingtack, Piccotac), polyterpene(Zonarez, Nirez, Piccolyte, Sylvatac), glycerol ester of rosin (Foral),pentaerythritol ester of rosin (Pentalyn), saturated alicyclichydrocarbon (Arkon P), coumarone indene, hydrocarbon (Picco 6000,Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035), and thelike.

The adhesion properties of the invention gels can also be determined bymeasuring comparable rolling ball tack distance “D” in cm using astandard diameter “d” in mm stainless steel ball rolling off an inclinedof height “H” in cm. Adhesion can also be measured by determining theaverage force required to perform 180° C. peel of a heat formed G1M1 oneinch width sample applied at room temperature to a substrate M2 to formthe composite M1G1M2. The peel at a selected standard rate cross-headseparation speed of 25 cm/minute at room temperature is initiated at theG1M2 interface of the M1G1M2 composite, where the substrate M2 can beany of the substrates mentioned and M1 preferably a flexible fabric,metal surface.

Other cold applied adherent gels to teflon type polymers: TFE, PTFE,PEA, FEP, etc., polysiloxane as substrates are achieved using theadherent invention gel. Likewise, adherent invention gel substratecomposites can be both formed by casting hot onto a substrate and thenafter cooling adhering the opposite side of the adherent gel to asubstrate having a low melting point. Two or more invention gels ofdifferent rigidity, of different gel polymer blends, of differentselected material containing invention gels can be formed to form GnGn,Gn,Gn,Gn, and the like composites. The adherent gel is most essentialwhen it is not possible to introduce heat in an heat sensitive orexplosive environment or in outer space. The use of solid or liquidresins promotes adherent gel adhesion to various substrates both whilethe adherent gel is applied hot or at room temperature or below or evenunder water. The adherent invention gels can be applied without heatingto paper, foam, plastic, fabric, metal, concrete, wood, wire screen,refractory material, glass, synthetic resin, synthetic fibers, and thelike.

The substrate materials include selected from the group consisting ofpaper, foam, plastic, fabric, metal, metal foil, concrete, wood, glass,various natural and synthetic fibers, including glass fibers, ceramics,synthetic resin, and refractory materials. The invention gels can becasted unto substrates, such as open cell materials, metals, ceramics,glasses, and plastics, elastomers, fluropolymers, expandedfluropolymers, Teflon (TEE, PTE, PEA, FEP, etc), expanded Teflon, spongyexpanded nylon, etc.; the molten gel composition is deformed as it isbeing cooled. Useful open-cell plastics include: polyamides, polyimides,polyesters, polyisocyanurates, polyisocyanates, polyurethanes,poly(vinyl alcohol), etc. Open-celled Plastic (sponges) suitable for usewith the compositions are described in “Expanded Plastics and RelatedProducts”, Chemical Technology Review No. 221, Noyes Data Corp., 1983,and “ Applied Polymer Science”, Organic Coatings and Plastic Chemistry,1975. These publications are incorporated herein by reference.

In my U.S. Pat. No. 5,760,117, is described a non-adhering gel which ismade non-adhering, by incorporating an advantage amount of stearicacids. The gels of this invention can be formulated with metal stearatesto decrease tack (e.g., aluminum stearate, barium stearate, calciumstearate, lithium stearate, magnesium stearate, potassium stearate,sodium stearate, strontium stearate, zinc stearate, polyethylene glycoldistearate, polypropylene glycol ester or fatty acid, andpolytetramethylene oxide glycol distearate, waxes, stearic acid. Suchnon-adhering gels by including additives are no longer optical clear andwith time some of the additives can blooms uncontrollably to the gelsurface, much less so, when formed with gels of controlled distributionSEB/SEBS copolymers.

As described at pages 23-27 of copending applications U.S. Ser. No.09/285,809 and pages 20-23 of U.S. Ser. No. 09/274,498 incorporated byreference above, polyphenolics with one or more sterically hinderedphenolic hydroxyl groups when incorporated into the invention gels willresult in the appearance of large crystals in the interior as well as onthe surface of the gels. The crystals have no effect on the high COF ofthe resulting gels. When selected amounts of internal nucleating agentsare incorporated in the invention gels in combination with selectedamounts of one or more of a low coefficient of friction (COF) agents,the large crystals no longer forms within the gels; and the surface ofthe gels exhibit lower and lower COF with time. Bringing the gels incontact with selected external nucleating agents decreases the time ortotally eliminates the time needed for the gel's outer surface toexhibit a low COF.

The gels and soft elastomers incorporating low COF agents and internaland/or external nucleating agents exhibit a much lower coefficient offriction when measured in contact with a reference surface than gels andsoft elastomers made without such components. School book physicsteaches COF can be determined experimentally, for two given surfacesthat are dry and not lubricated, the ratio of the tangential forceneeded to overcome the friction to the normal force which holds the twosurfaces in contact (e.g., the weight of a block of gel or elastomermaterial on a surface) is a constant independent of the area or of thevelocity with which the surfaces (surface of a side of the block incontact with another surface) move over wide limits. This ratio is μ,the coefficient of friction. The coefficient of sliding friction for ablock of material beingμ=(f/Fn)where f is the force of friction, and Fn the normal force. For the caseof the block on the horizontal table, if m is the mass of the block,then mg is the normal force and the above equation can be written asμ=f/mg

In the case the block of a block rests on a board, originallyhorizontal, and that the board then is tilted until a limiting angle øis reached, beyond which the block will begin to slide down the board.At this angle the component of the weight of the object along the boardis just equal in amount to that necessary to overcome the force offriction. The force down the plane is mg sin ø, while the normal forceis mg cos ø. Therefore we haveμ=(mg sin ø)/(mg cos ø) or μ=tan ø.

The limiting value of ø for which μ=tan ø is true is call the angle ofrepose. Measurement of the tangent of this angle will give thecoefficient of friction of the contacting surfaces of the block and theboard that slide one upon the other. As an example of low COF agentsadvantageously useful in soft thermoplastic elastomers and gels,excellent results is achieved with 50 grams of a polyphenolic withsterically hindered phenolic hydroxyl groups (Irganox 1010), about 100grams of one or more nucleating agents (such as very fine particle sizesodium benzoate, dibenzylidene sorbitol, its alkylated derivatives,talc, zinc sterate, amorphous silica, aluminum sterate, etc.) and 5,000grams of S-EB-S and 25,000 gram of oil. The same excellent result isachieved when S-EB-S is adjusted to 3,000 grams, 4,000 grams, etc. Thesame result is achieved with copolymers as well as in combination withother polymers. Moreover, when about 50 grams of tetrakis[methylene3,-(3′5′-di-tertbutyl-4″ hydroxyphenyl) propionate] methane is use (perabout 22.68 Kilograms or 50 lbs of gel) as a low COF agent, tack iscompletely removed from the surface of the gel after two to three weeksof blooming.

When this is repeated with an external nucleating agent, such as withvarious fine particles for coating the outside surface of the elastomeror gel which fine particles can also be useful for removing tack, suchas with talc, metal stearates including aluminum sterate, calciumstearate, zinc sterate, amorphous silica, fine flour, corn starch, finesoil, fine sand, fine metallic powder, vacuum dusk fine wood dusts andthe like, lower COF of the gel surface by internal nucleating agents canbe achieved within a few days to less than several hours. After coatingthe gel for the desired period of time, the fine polar and water solubleparticles can be washed off with water and soap, while non-polar andnon-water soluble fine powders including talc can be removed by wearingit off or by lifting it off with the use of adhesive tapes if sodesired.

What is the surface properties of low CFO agents at theair/plasticizer-copolymer interface? Theory notwithstanding, theresulting gel surface will comprise of very fine molecular segments oreven very fine crystal grains of low COF agents confined at theair/plasticizer and polymer interface. Depending on concentration, thenon-polar segments of the low COF agents will have a tendency of beingadsorbed by the predominate plasticizer and copolymer midblock phase atthe gel surface. The slightly polar or more polar segments of the lowCOF agents are adsorbed to a lesser extent by the plasticizer-copolymersurface. This is supported by observing the water wettingcharacteristics at the gel surface with and with out low COF agents atthe air gel surface interface. A drop of water will bead up and notreadily wet the gel surface free of any low COF agents (hydrophobic).The presence of even slightly polar low COF agents exposed on thesurface of the gel will make a drop of water flatten out and not bead upwhen place on the gel surface (hydrophilic).

Commercial high melting point low oil solubility, and polar low COFagents such as polyphenolics which are advantageously useful in thepresent invention include: Ethanox 330 (Ethyl), Irganox 1010(Ciba-Geigy), Santechhem A/O 15-1 (Santech), Ultra 210 (GE), Hostanox 03(Hoechst Celanese), Irganox 3114 (Ciba-Geigy), Mixxim AO-3 (Fairmont),and the like. Other high melting point, low oil solubility, polar lowCOF agents contemplated are common amino acids: Such As Alamine,Arginine, Asparagine, Aspartic Acid, Cysteine, Glutamine, Glutamic Acid,Glycine, Histidine, Isoleucine, Leucine, Lysine, Methionine,Phenylalanine, Proline, Serine, Threonine, Tryptophan, Tyrosine andValine. The melting points of these amino acids range from about 178° C.to about 344° C. The amino acids having greater advantage serving as lowCOF agents are Asparagine, Aspartic acid. Glutamine, Glutamic acid,Tryptophan, and Tyrosine.

Copolymer for forming the low COF compositions include block copolymers,random copolymers, metallocene catalyzed ethylene-styrene copolymers,Low COF gels made from thermoplastic elastomer copolymers and blockcopolymers having one or more substantially crystalline polyethylenesegments or midblocks. The low COF gels advantageously exhibit high,higher, and higher, and ever higher tear resistance than realized beforeas well as improved high tensile strength. The low COF gels also exhibitimproved damage tolerance, crack propagation resistance and especiallyimproved resistance to high stress rupture which combination ofproperties makes the gels advantageously and surprisingly suitable forany desired use including fishing bait toys, inflatable air cushions inautomobiles, and the like. The invention gels are advantageously usefulfor making low COF gel compositions. Moreover, various polymer gels madefrom linear triblock copolymers, multi-arm block copolymers, branchedblock copolymers, radial block copolymers, multiblock copolymers,random/non-random copolymers, thermoplastic crystalline polyurethanecopolymers with hydrocarbon midblocks or mixtures of two or more of suchcopolymers can also be made with low COF.

The low tack negligible tack, and no tack properties of the inventiongels, invention gel composites, and invention articles are in theory canbe achieved by the presence of small amounts of the low viscosity, lowIBP plasticizers. The presence of about any measured amount(s) ofselected low viscosity, low IBP plasticizers can impart low tack orreduce tackiness to the invention gels and invention gel articles.

Independently (as taught in my application U.S. Ser. No. 09/285,809),the presence of low molecular weight polystyrene or block copolymers ofhigher styrene end block content can impart a lower tack or a reductionin the invention gels' tackiness at any selected plasticizerviscosities. The combination of greater polystyrene end block contentand the presence of lower plasticizer viscosity can further decrease theinvention gel articles' tackiness. Invention gels using block copolymerswith polystyrene end block content of 33 can exhibit less tack than whenusing a block copolymer with a styrene content of 30. Invention gelsusing block copolymers with polystyrene end block content of 35 canexhibit less tack than when using a block copolymer with a styrenecontent of 33. Invention gels using block copolymers with polystyreneend block content of 37 can exhibit less tack than when using a blockcopolymer with a styrene content of 35. Block copolymers with styrenecontent or added low molecular weight polystyrene greater than 33 iscapable of reducing the invention gels' tackiness. Useful levels ofstyrene content include 34, 35, 36, 37, 38, 39, and higher. Usefullevels of interpolymer E-S-E, poly(ethylene-styrene) (ES) whenincorporated in the invention gels can decrease invention gel tack bythe contribution of the E-S-E's ethylene and styrene components to theover all increasing styrene content and decrease invention gel tackinessby increasing the over all ethylene crystallinity.

For example, S Ethylene-styrene copolymers ES30 and ES44 having styrenewt % of 39.6 & 43.9 respectively can be used in selected minor amountsto reduce tack because of their higher styrene content M type copolymersES53, ES58, ES62, ES63, and ES69 having styrene wt % of 52.5, 58.1,62.7, 62.8, and 69.2 respectively and crystallinity, %, DSC, based oncopolymer of 37.5, 26.6, 17.4, 22.9, 19.6 and 5.0 respectively can beuse in minor amounts to reduce tack because of their high styrenecontent and higher crystallinity. S type copolymers ES72, ES73, and ES74with styrene wt % of 72.7, 72.8, and 74.3 respectively can be used invery selected minor amounts to reduce tack because of their even higherstyrene content. The minor amounts of ethylene-styrene copolymers canrange from less than about 1% of the total 100 parts by weight ofcopolymer to greater than about 10% for tack reduction. Otherinterpolymers with corresponding styrene and crystallinity content aspoly(ethylene-styrene) (ES) that can be use include:poly(ethylene-styrene-propylene) (ESP),poly(ethylene-styrene4-methyl-1-pentene) (ES4M1P),poly(ethylene-styrene-hexend-1) (ESH1), poly(ethylene-styrene-octene-1)(ESO1), and poly(ethylene-styrene-norborene) (ESN),poly(ethylene-alpha-methylstyrene-propylene),poly(ethylene-alpha-methylstyrene-4-methyl-1-pentene),poly(ethylene-alpha-methylstyrene-hexend-1), poly(ethylene-alpha-methylstyrene-octene-1), and poly(ethylene-alpha-methylstyrene-norborene) andthe like.

The use of selected plasticizers described above can decrease or impartno tack to the invention gels and invention gel articles. The inventiongel can be made non tacky to the touch and can be quantified using asimple test by taking a freshly cut Gel probe of a selected gel rigiditymade from the invention gel. The gel probe is a substantially uniformcylindrical shape of length “L” of at least about 3.0 cm formedcomponents (1)-(3) of the invention gel in a 16×150 mm test tube. Thegel probe so formed has a 16 mm diameter hemi-spherical tip which (notunlike the shape of a human finger tip) is brought into perpendicularcontact about substantially the center of the top cover of a new,untouched polystyrene reference surface (for example the top coversurface of a sterile polystyrene petri dish) having a diameter of 100 mmand a weight of 7.6 gram resting on its thin circular edge (whichminimizes the vacuum or partial pressure effects of one flat surface incontact with another flat surface) on the flat surface of a scale whichscale is tare to zero. The probe's hemi-spherical tip is place incontact with the center of the top of the petri dish cover surface andallowed to remain in contact by the weight of the gel probe while heldin the upright position and then lifted up. Observation is maderegarding the probe's tackiness with respect to the clean referencepolystyrene surface. For purpose of the foregoing reference tack testtackiness level 0 means the polystyrene dish cover is not lifted fromthe scale by the probe and the scale shows substantially an equalpositive weight and negative weight swings before settling again back tozero with the swing indicated in (negative) grams being less than 1.0gram. A tackiness level of one 1, means a negative swing of greater than1.0 gram but less than 2.0 gram, tackiness level 2, means a negativeswing of greater than 2 gram but less than 3 gram, tackiness level 3,means a negative swing of greater than 3 gram but less than 4 gram,before settling back to the zero tare position or reading. Likewise,when the negative weight swing of the scale is greater than the weightof the dish (i.e., for the example referred above, greater than 7.6gram), then the scale should correctly read-7.6 gram which indicates thedish has completely been lifted off the surface of the scale. Such anevent would demonstrate the tackiness of a gel probe having sufficienttack on the probe surface. The invention gel fails to lift off thepolystyrene reference from the surface of the scale when subject to theforegoing reference tack test. Advantageously, the invention gel canregister a tackiness level of less than 5, more advantageously, lessthan 3, still more advantageously, less than 2, and still moreadvantageously less than 1. The non-tackiness of the invention gel canadvantageously range from less than 6 to less than 0.5 grams, typicaltack levels are less than 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0,1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.5,2.8, 3.0, 3.5, 4.0, 4.5, 5.0 grams and the like. Whereas probes of gelsmade from amorphous gels such as SEPS, SEBS, S-EP-EB-S, and the likewith copolymer styrene to rubber ratio of less than 37:63 andplasticizer of higher than 30 cSt 40° C. are found to lift thepolystyrene reference from the surface of the scale. For purposes ofindicating tack, the method above can provide gel tack level readings of1, 2, 3, 4, 5, 6, and 7 grams. More accurate and sensitive readings canbe made using electronic scales of tack levels of less than 1 gram. Bythis simple method tack levels (of a gel probe on a polystyrenereference surface) can be measure in terms of gram weight displacementof a scale initially tare to zero. For purpose of the present inventionthe method of using a polystyrene reference surface having a weight of7.6 grams in contact and being lifted by the tackiness of a cylindricalgel probe having a 16 mm diameter hemi-spherical tip is used todetermine the tackiness of the invention gel. The level of tack beingmeasured in gram Tack at 23° C.

Non tacky is defined for the purpose of the invention gel as the feelingregistered in the mind by the sense of touch of the fingers of the humanhand. An reinforcing observation is that a non tacky reference gelsample does not cling or stick to the fingers under its own weight whenthe force of holding the reference gel sample between the fingers isreleased and the sample is allowed to fall by the action of gravity. Asimple way to accurately measure the non tacky feeling as sensed by thefingers is to drop a reference gel sample having a cylindrical shape ofabout 1.0 cm diameter and 1.0 cm in length a distance of 10 cm on to thesurface of a polystyrene petri dish having a diameter of 10 cm inclinedat 45. The reference gel sample is considered non tacky if it (1)“bounce at least twice before coming to rest”, (2) “bounce off”, (3)“bounce and then rolls off”, or (4) “rolls off” on striking thepolystyrene surface. If none of (1) thru (4) is observed, then the levelof Gram Tack can be determined by the gel sample method above.

The invention gels can be made to exhibit sufficient low Gram Tack to benoticeable non-tacky to the touch of the fingers of a typical human handat 23° C. A simple way to accurately measure the non tacky feeling assensed by the fingers is to drop a reference gel sample having acylindrical shape of about 1.0 cm diameter and 1.0 cm in length adistance of 10 cm on to the surface of a polystyrene petri dish having adiameter of 10 cm inclined at 45′. The reference gel sample isconsidered non tacky if it (1) “bounce at least twice before coming torest”, (2) “bounce off”, (3) “bounce and then rolls off”, or (4) “rollsoff” on striking the polystyrene surface. If none of (1) thru (4) isobserved, then the level of Gram Tack can be determined by the gelsample method above. Other methods of testing tack is by conventionalrolling ball tack.

The gels can be made non-adhering, non-sticking, non-tacky by usingmajor or minor amounts of one or more low viscosity plasticizers. On theother hand, the molten gelatinous elastomer composition will adheresufficiently to certain plastics (e.g. acrylic, ethylene copolymers,nylon, polybutylene, polycarbonate, polystyrene, polyester,polyethylene, polypropylene, styrene copolymers, and the like) providedthe temperature of the molten gelatinous elastomer composition issufficient high to fuse or nearly fuse with the plastic. In order toobtain sufficient adhesion to glass, ceramics, or certain metals,sufficient temperature is also required (e.g. above 250° F.).

Glassy phase associating homopolymers such as polystyrene and aromaticresins having low molecular weights of from about 2,500 to about 90,000can be blended with the triblock copolymers of the invention in largeamounts with or without the addition of plasticizer to provide acopolymer-resin alloy of high impact strengths. More advantageously,when blended with multiblock copolymers and substantially randomcopolymers the impact strengths can be even higher. The impact strengthof blends of from about 150 to about 1,500 parts by weight glass phaseassociating polymer and resins to 100 parts by weight of one or moremultiblock copolymers can provide impact strength approaching those ofsoft metals. At the higher loadings, the impact strength approaches thatof polycarbonates of about 12 ft-lb/in notch and higher.

Improved lower compression set, improved lower heat distortion set canbe achieved by increasing the styrene content of the block copolymers orby increasing the over all styrene content forming the invention gelsand invention gel articles. The increase in styrene content willincreased the force needed for elongating the invention gels' thanabsent the additional amount of polystyrene. Improvements in lower setcan also be achieved by increasing the polyethylene crystallinity of theblock copolymers or by increasing the over all polyethylenecrystallinity forming the invention gels and invention gel articles.Improvements in lower set can also be achieved by incorporatingplasticizers having higher, and higher viscosities with or without lowerand lower viscosity plasticizers for improve lower gel tack.

The use of selected plasticizers as described above can improvecompression heat set in the invention gels and invention gel articles.The requirements of the invention gels for use as fishing bait are many.The invention gels when made to feel non-tacky in the hand are suitablefor forming articles for use outdoors (excellent for exposure toenvironmental extremes) requiring properties suitable for use under highstress, elongation, extremes of indoor and outdoor temperatures asinside the fishermen's tickle box placed in the hot Sun. Summer heat canreach above about 90° F. to about 133° F. or higher inside an automobileor fishing metal or plastic tackle box. The invention gels are suitablefor fishing presentations in fresh as well as in salt waters. Theinvention gels can be made with selectively low or soft to high gelrigidities and can be orientated and multiple colored for specialeffects. Additives can be incorporated internally or externally tocontrollably remove, increase or decrease tack, to controllably increaseor decrease compression set, heat set, and distortion or deflectionunder load, to controllably increase or decrease elongation, tocontrollably increase or decrease rigidity, to controllably increase ordecrease tear resistance, and the like to modify or produce any desiredproperties of the invention gels.

The invention gel can also contain useful amounts of conventionallyemployed additives such as stabilizers, antioxidants, antiblockingagents, colorants, fragrances, flame retardants, other polymers in minoramounts and the like to an extend not affecting or substantiallydecreasing the desired properties of the present invention. The presentinvention gel can also contain useful amounts of conventionally employedadditives such as stabilizers, antioxidants, antiblocking agents,colorants, fragrances, flame retardants, flavors, other polymers inminor amounts and the like to an extend not affecting or substantiallydecreasing the desired properties. Additives useful in the gel of thepresent invention include: barium ferrite,(1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl]benzene),4,4″-methylenebis(2,6-di-tert-butylphenol),4,4″-methylenebis(2,6-di-tert-butylphenol), alkylated aromatichydrocarbon, aluminates, aluminatrihydrate, aluminum and brass flakes,aluminum sterate, amorphous silica, antiblocking agents, antimony oxide,azo pigments, barium ferrite, behenamide, blowing agents includingwater, calcium sterate, carbon blacks, ceramic pigments, Chimassorb 119,944, 2020, chromium dioxide, clay, coumarone indene,distearyl-pentaerythritol-diproprionate, erucamide, erucyl erucamide,erucyl stearamide, feldspar, fine metallic powder, flame retardants;fluorescent dyes, gas bubbles formed by inert gases, glass, glycerolester of rosin, hydrocarbon resins, hydrophobic or hydrophilic surfacedepending on additives, internal and external tack modifiers, Irganox245, 1076, 1098, 1135, 5057, HP series: 2215, 2225, 2921, 2411, 136;iron cobalt oxides, iron oxides (Fe3O4,-Fe2O3, etc.), iron, ironblues,lake pigments, magnetic particle materials, metal flakes, metallicpigments, mica, microspheres, mixed olefin, molybdenum, silicone fluids,N,N″-ethylenebisoleamide, N,N″-ethylenebisstearamide, non-adhering,non-sticking modifiers, octadecyl3-(3″,5″-di-tert-butyl-4″-hydroxyphenyl) propionate, oleamide, oleicacid, oleyl palmitamide, other metal sterates, particulate fillers,pentaerythritol ester of rosin, phosphorescent pigments, phthalocynines,pigments, polyalphamethylstyrene/vinyl toluene copolymer, polymerizedmixed olefins, polystyrene, polyterpene, saturated alicyclic,hydrocarbons, silica, silicon dioxide, silicone fluids, stearamide,stearic acid, sterryl erucaride, strontium ferrite, talc,tetrakis[methylene 3,-(3′5′-di-tertbutyl-4″-hydroxyphenyl)propionate]methane, thiodiethylene bis-(3,5-ter-butyl4-hydroxy)hydrocinnamate, Tinuvin P, 123, 144, 213, 234, 326, 327, 328, 571, 622,770, 765; TiO2, ultramarines, Uvitex OB, waxes (e.g. polyethylene,polypropylene, microcrystalline, carnauba, paraffin, montan, candelilla,beeswax, ozokerite, ceresine, and the like), wollastonite, zinc sterate,and the like. The report of the committee on Magnetic Materials,Publication NMAB426, National Academy Press (1985) is incorporatedherein by reference.

The invention gels are also suitable for forming composites combinationswith various substrates. Another embodiment of the invention is acomposite comprising: a gel denoted by G, being in adherent contactadhesive contact clinging contact fastening contact, sticking contactphysical contact, or physically interlocking contact with a selectedmaterial M to form composites as denoted for simplicity by theircombinations GnGn, GnMn, GnMnGn, MnGnMn, MnGnGn, GnGnMn, MnMnGn,MnMnMnGn, MnMnMnGnMn, MnGnGnMn, GnMnGnGn, GnMnMnGn, GnMnMnGn, GnGnMn Mn,GnGnMn GnMn, GnMnGnGn, GnGnMn, GnMnGnMnMn, MnGnMn GnMnGn, GnGnMnMnGn,GnGnMnGnMn Gn, and the like or any of their permutations of one or moreGn with Mn and the like, wherein when n is a subscript of M, n is thesame or different selected from the group consisting of foam, plastic,fabric, metal, concrete, wood, glass, ceramics, synthetic resin,synthetic fibers or refractory materials and the like; wherein when n isa subscript of G, n denotes the same or a different gel rigidity of fromless than about 2 gram to about 1,800 gram Bloom and higher).

Furthermore, the interlocking materials with the gel of the inventionmay be made from flexible materials, such as fibers and fabrics ofcotton, flax, and silk. Other flexible materials include: elastomers,fiber-reinforced composites, mohair, and wool. Useful synthetic fibersinclude: acetate, acrylic, aremid, glass, modacrylic polyethylene,nylon, olefin, polyester, rayon, spandex, carbon, sufar,polybenzimidazole, and combinations of the above. Useful open-cellplastics include: polyamides, polyimides, polyesters, polyisocyanurates,polyisocyanates, polyurethanes, poly(vinyl alcohol), etc. Open-celledPlastic (foams) suitable for use with the compositions of the inventionare described in “Expanded Plastics and Related Products”, ChemicalTechnology Review No. 221, Noyes Data Corp., 1983, and “ Applied PolymerScience”, Organic Coatings and Plastic Chemistry, 1975. Thesepublications are incorporated herein by reference. These include: openand non-opened cell silicone, polyurethane, polyethylene, neoprene,polyvinyl chloride, polyimide, metal, ceramic, polyether, polyester,polystyrene, polypropylene. Example of such foams are: Thanol®, Arcol®,Ugipol®, Arcel®, Arpak®, Arpro®, Arsan®, Dylite®, Dytherm®, Styrofoam®,Trymer®, Dow Ethafoam®, Ensolite®, Scotfoam®, Pyrell®, Volana®,Trocellen®, Minicel®, and the like.

Sandwiches of gel-material (i.e. gel-material-gel ormaterial-gel-material, etc.) are useful as dental floss, shockabsorbers, acoustical isolators, vibration dampers, vibration isolators,and wrappers. For example the vibration isolators can be use underresearch microscopes, office equipment tables, and the like to removebackground vibrations. The tear resistance nature of the invention gelsare superior in performance to triblock copolymer gels which are muchless resistance to crack propagation caused by long term continuedynamic loadings.

Adhesion to substrates is most desirable when it is necessary to applythe adherent invention gels to substrates in the absence of heat or onto a low temperature melting point substrate for later peel off afteruse, such as for sound damping of a adherent invention gel compositeapplied to a first surface and later removed for use on a secondsurface. The low melting substrate materials which can not be exposed tothe high heat of the molten adherent invention gels, such as low meltingmetals, low melting plastics (polyethylene, PVC, PVE, PVA, and the like)can only be formed by applying the adherent invention gels to thetemperature sensitive substrates. Other low melting plastics include:polyolefins such as polyethylene, polyethylene copolymers, ethylenealpha-olefin resin, ultra low density ethylene-octene-1 copolymers,copolymers of ethylene and hexene, polypropylene, and etc.

The use of selected plasticizers as described above can promote adhesionof the invention gels and invention gel articles to selected substratesof the invention to form composite gel articles.

The invention gels, gel composites, gel composite blends can be madewith or without one or more additional polymers and selected materialadditives selected from the group consisting of polyisobutyleneincluding polybutene, elastomeric diblock copolymers ofpoly(styrene-butadiene)n, poly(styrene-isoprene)n,poly(styrene-ethylene-propylene)n, or poly(styrene-ethylene-butylene)n,poly(styrene-butadiene)n, poly(styrene-isoprene)n,poly(styrene-ethylene-propylene)n, or poly(styrene-ethylene-butylene)n,poly(styrene-ethylene-propylene), poly(styrene-ethylene-butylene);others include additive selected from the group consisting ofhydrocarbon resins, polyisobutylene including polybutene, additionalblock copolymers of poly(styrene-isoprene-styrene),poly(styrene-butadiene-styrene), poly(styrene-butadiene)n,poly(styrene-isoprene)n, poly(styrene-ethylene-propylene)n,poly(ethylene-styrene), poly(styrene-ethylene-butylene)n, butadienerubber, poly(ethylene/propylene), and poly(ethylene/butylene); anadditive selected from the group consisting ofpoly(styrene-butadiene-styrene), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene,polyethylene, diblock copolymers of poly(styrene-butadiene)n,poly(styrene-isoprene)n, poly(styrene-ethylene-propylene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)n,poly(styrene ethylene-butylene)_(n), ethylene-styrene interpolymers(ESI), and the like.

The gels have many uses as described in my other applications andpatents (incorporated by reference above) which uses include fishingbait, antagonist muscle toning suit, bone promoting suit bone lossprevention suit, exercise suit, exercise swim suit, de-iceing componentfor snow boards and ski boards, anti fouling coating for ocean vessels,zero gravity suit, toys as disclosed in my U.S. Pat. Nos. 5,624,294,5,938,499 and 6,033,283, flying toys as disclosed in my patents Pat.Nos. 5,324,222, 5,868,597, and Pat. Nos. 5,655,947, 6,050,871, exerciseband, and the like. Which patents and applications are incorporatedherein by reference.

The invention gels is excellent for cast molding and the molded productshave various excellent characteristics which cannot be anticipated formthe properties of the raw components. Other conventional methods offorming the gel compositions can be utilized, including cast molding,extruding, extrusion molding, fiber forming film forming and spinmolding.

The high viscosity SEEPS type block copolymers with-E-midblock canachieve improvements in one or more physical properties includingimproved damage tolerance, improved crack propagation resistance,improved tear resistance, improved resistance to fatigue of the bulk geland resistance to catastrophic fatigue failure of gel composites, suchas between the surfaces of the gel and substrate or at the interfaces ofthe interlocking material(s) and gel, which improvements are not foundin amorphous gels at corresponding gel rigidities.

As an example, when fabric interlocked or saturated with amorphousS-EB-S gels (gel composites) are used as gel liners for lower limb orabove the knee prosthesis to reduce pain over pressure areas and giverelief to the amputee, the commonly used amorphous gels forming theliners can tear or rip apart during marathon race walk after 50-70miles. In extended use, the amorphous gels can rip on the bottom of theliner in normal race walk training of 40-60 miles over a six weeksperiod. In such demanding applications, the invention gels areespecially advantageous and is found to have greater tear resistance andresistance to fatigue resulting from a large number of deformationcycles than amorphous gels-The invention gels are also useful forforming various orthotics and prosthetic articles such as for lowerextremity prosthesis of the L5664 (lower extremity socket insert, aboveknee), L5665 (socket insert, multi-durometer, below knee), L5666 (belowknee, cuff suspension interface), L5667 (below knee, above knee, socketinsert, suction suspension with locking mechanism) type devices asdescribed by the American Orthotic & Prosthetic Association (AOPA)codes. The invention gels are useful for making AOPA code devices forupper extremity prosthetics. The devices can be cast molded or injectionmolded in combination with or without fiber or fabric backing or fiberor fabric reinforcement. When such liners are made without fabricbacking, various invention gels can be used to form gel-gel andgel-gel-gel composites and the like with varying gel rigidities for thedifferent gel layer(s).

Health care devices such as face masks for treatment of sleep disorderrequire non tacky invention gel. The gel forming a gel overlap portionon the face cup at its edge conforming to the face and serve to providecomfort and maintain partial air or oxygen pressure when worm on theface during sleep. Although tacky gels can be made from the inventiongel, tacky gels because of its tactile feel are undesirable for suchapplications as face masks and other prolong skin contact uses.

The invention gel can be formed into gel strands, gel bands, gel tapes,gel sheets, and other articles of manufacture in combination with orwithout other substrates or materials such as natural or syntheticfibers, multifibers, fabrics, films and the like. Moreover, because oftheir improved tear resistance and resistance to fatigue, the inventiongels exhibit versatility as balloons for medical uses, such as balloonfor valvuloplasty of the mitral valve, gastrointestinal balloon dilator,esophageal balloon dilator, dilating balloon catheter use in coronaryangiogram and the like. Since the invention gels are more tear resistantthey are especially useful for making condoms, toy balloons, andsurgical and examination gloves. As toy balloons, the invention gels aresafer because it will not rupture or explode when punctured as wouldlatex balloons which often times cause injures or death to children bychoking from pieces of latex rubber. The invention gels areadvantageously useful for making gloves, thin gloves for surgery andexamination and thicker gloves for vibration damping which preventsdamage to blood capillaries in the fingers and hand caused by handlingstrong shock and vibrating equipment. Various other gel articles can bemade from the advantageously tear resistant invention gels and inventiongel composites of the inventions include gel suction sockets, andsuspension belts.

The invention gels are also useful for forming orthotics and prostheticarticles such as for lower extremity prosthesis described below. Porous,webbing or matting that are skin breathe-able comprising the inventiongel strands can be formed into a webs or matting by cold formingsandwiched gel strand-composites using alkyl cyanoacrylates such asethyl, butyl, methyl, propyl cyanoacrylates and the like. The alkylcyanoacrylates (AC) will interlock with the soft gelatinous elastomercomposition of the invention, thereby resulting in gel-(AC)-gelcomposite webbing or matting articles. Alkyl cyanoacrylates are usefulfor interlocking gel of the invention with other substrates such aspottery, porcelain, wood, metal, plastics, such as acrylics, ABS, EPDM,nylon Fiberglass, phenoics, plexiglass, polycarbonate, polyesters,polystyrene, PVC, urethanes and the like. Other cyanoacrylates such ascyanoacrylate ester are inhibited and do not interlock with theinvention gels.

In applications where extreme tear resistance, low rigidity, highelongation, good compression set and excellent tensile strength areimportant the invention gels would be advantageous. The invention gelscan be formed into any desired shaped, size and thickness suitable as acushion; the shaped composition can be additionally surrounded withfilm, fabric, foam, or any other desired material or combinationsthereof. The original shape can be deformed into another shape (tocontact a regular or irregular surface) by pressure and upon removal ofthe applied pressure, the composition in the deformed shape will recoverback to its original shape. A cushion can be made by forming thecomposition into a selected shape matching the contours of the specificbody part or body region. Moreover, the composition can be casted ontosuch materials, provided such materials substantially maintain theirintegrity (shape, appearance, texture, etc.) during the casting process.The same applies for brace cushions for the hand, wrist finger, forearm,knee, leg, etc.

Other uses include: shaped articles as toys, optical uses (e.g. claddingfor cushioning optical fibers from bending stresses) and various opticaldevices, as lint removers, dental floss, as tips for swabs, as softelastic fishing baits, as a high vacuum seal (against atmospherepressure) which contains a useful amount of a mineral oil-based magneticfluid particles, in the form of (casted, extruded, or spun formed)threads, strips, yarns, strands, tapes which can be weave into cloths,fine or coarse fabrics. Still other uses include: games; novelty, orsouvenir items; elastomeric lenses, light conducing articles, opticalfiber connectors; athletic and sports equipment and articles; medicalequipment and articles including derma use and for the examination of oruse in normal or natural body orifices, health care articles; artistmaterials and models, special effects; articles designed for individualpersonal care, including occupational therapy, psychiatric, orthopedic,podiatric, prosthetic, orthodontic and dental care; apparel or otheritems for wear by and on individuals including insulating gels of thecold weather wear such as boots, face mask, gloves, full body wear, andthe like have as an essential, direct contact with the skin of the bodycapable of substantially preventing, controlling or selectivelyfacilitating the production of moisture from selected parts of the skinof the body such as the forehead, neck, foot, underarm, etc; cushions,bedding, pillows, paddings and bandages for comfort or to preventpersonal injury to persons or animals; house wares and luggage; vehicleimpact deployable air bag cushions; medical derma use and for themedical examination through surgical orifices of the human body, healthcare articles, artist materials and models, special effects, articlesdesigned for individual personal care, including occupational therapy,psychiatric, orthopedic, podiatric, prosthetic, orthodontic and dentalcare, apparel or other items for wear by and on individuals includinginsulating invention gels of the cold weather wear such as boots, facemask, gloves, full body wear in direct contact with the skin of the bodycapable of substantially preventing, controlling or selectivelyfacilitating the production of moisture from selected parts of the skinof the body such as the forehead, neck, foot underarm, etc; cushions,bedding, pillows, paddings and bandages for comfort or to preventpersonal injury to persons or animals, as articles useful intelecommunication, electrical utility, industrial and food processing,in low frequency vibration applications, such as viscoelastic layers inconstrained-layer damping of mechanical structures and goods, asviscoelastic layers used in laminates for isolation of acoustical andmechanical noise, as anti-vibration elastic support for transportingshock sensitive loads, as vibration isolators for an optical table, asviscoelastic layers used in wrappings, enclosures and linings to controlsound, as compositions for use in shock and dielectric encapsulation ofoptical, electrical, and electronic components, as molded shape articlesfor use in medical and sport health care, such use include therapeutichand exercising grips, dental floss, crutch cushions, cervical pillows,bed wedge pillows, leg rest, neck cushion, mattress, bed pads, elbowpadding, dermal pads, wheelchair cushions, helmet liner, cold and hotpacks, exercise weight belts, traction pads and belts, cushions forsplints, slings, and braces (for the hand, wrist finger, forearm, knee,leg, clavicle, shoulder, foot, ankle, neck, back, rib, etc.), and alsosoles for orthopedic shoes.

Still the invention gels can have many other uses, these include:absorbing gel is a gel capable of absorbing polar liquids from a solidcontaining same; acetate fiber gel is a gel containing acetate fibers;acrylic gel is a gel containing acrylic fibers; adhesive gel is a gelhaving adhesiveness to other surfaces; aero gel is a gel formed in anaerodynamic shape capable of flying; aerodynamic gel is a gel articlehaving aerodynamic characteristics; amino acid gel is a gel containingone or more amino acids; amorphous gel is a gel being amorphous;anti-cavitation gel is a gel layer or coating capable of reducing oreliminating bubble formation in a liquid in motion; anti-fouling gel isa gel coating resistant to marine fouling as on the bottom surface of aship; anti-freezing gel s a nonfreezing gel; anti-hydro dynamic drag gelis a gel body or coating which is slippery in water and capable ofreducing drag; other gels include: anti-slip gel; Aramid gel containingaramid fibers; Azion gel containing azion fibers; barrier gel is abarrier between liquids; solids; and gases made from a gel; bearing gelis a gel bearing capable of supporting a sliding; moving; rotating; andstatic load; bi-layer composite gel two or more layers of gels; biocompatible gel is a gel which is biologically compatible for medicaluse; bource fleece gel construction is a gel composite of gel and bourcefleece; burn treatment gel is a gel for treating burns by use of a gelcovering; camel hair gel construction gel containing camel hair; carbonfiber gel construction gel containing oriented carbon fibers; carbon gelis a gel containing carbon fibers or particles; cavitation gel is a geluse to prevent cavitation damage of metals; and other solids; ceramicgel is a gel which is loaded with compounded ceramic materials; clumpedpile gel construction composite of gel and clumped pile weaving; coldtemperature gel is a gel use at below STP in cold climates; compositegel is a composite having a gel as one or more components; compress gelis a gel use as a compress for needle injection or withdrawal at thesite of a vain; compression gel is a gel use in compression; conductivegel is a gel which is made heat or electrically conductive; cork gel isa gel compounded with fine cork particles; cotton gel is a gelcontaining cotton fibers; crunch gel is a gel with thin polyesterembedded sheets when squeezed produce a crunching sound; crystal gel isa gel having one or more components which exhibit crystallinity; cushiongel is a gel for cushion use; dampening gel is a energy damping gel forattenuating vibrational; mechanical motion; and sound; deodorantelimination gel is a gel containing deodorants; dielectric gel is a gelhaving dielectric electrical properties; dynamic gel is a gel resistantto fatigue under dynamic stress; edible gel is a shaped gel consumed asfood; electro gel is a gel containing a conductive amount of anelectrical conductor; exercise gel is a gel shaped as a band, rope,loop, or sheet for exercising; expansive gel; extreme cold weather gelis a gel use in low temperature conditions; fatigue resistant gel is agel resistant to fatigue; fatty acid gel is a gel containing one or morefatty acids; fiber directional gel is a gel containing one or moreoriented fibers; fiber gel is a gel containing one or more fibers; fiberlaminated gel is a gel laminate of fibers; fiber reinforced gel is a gelcontaining fibers which resists deformation in one or more directions;fire retardant gel is a gel containing one or more fire retardant; firmgel is a gel having a rigidity greater than 500 gram Bloom; fishing baitgel is a gel use for making fishing bait articles; fleece gelconstruction is a gel containing fleece; flesh-like gel is a gel havingrigidity similar to human flesh; floss gel is a gel use for flossing;food gel is a gel containing: fats, proteins, sugar, starch,carbohydrates, minerals, vitamins, and the like; other invention gelsinclude: friction reducing gel, gel composites, glass gel, goat hair gelconstruction, gravity gel, gripping gel, hand grip gel, hazard spillgel, heavy than water gel high temperature gel, high temperature gelcomposites, high velocity hydro gel, hydro projectile gel, hydrodynamicgel, hydrophobic gel, ice melting gel, ice-resistant gel, insulatinggel, kevlar gel construction, layered gel, lead gel, light barrier gel,light conductive gel, light scattering gel, light defusing gel, lightrefracting gel, lighter than water gel, liner gel, lint removing gel,lipid gel, liquidly gel, low drag gel, low temperature gel composites,magnetic gel, medical gel, membrane gel, memory gel, metallic gel, microfiber gel, mohair gel construction, multi layer gel, muscle gel,non-pill fleece gel construction, non-tacky gel, nozzle gel, nylon gel,optical gel, orientated fiber direction gel, oriented gel,pill-resistant gel construction, polar fleece gel construction,polyester gel, polytetrafluoroethylene gel construction, projectileprotection gel, protective coating gel, protective gel, protein gel,puffy gel, rabbit hair construction, ramie gel, random fiber gel, rayongel, reducing gel, reflective gel, refractive gel, release gel,resonating gel, robotic gel, scar treatment gel, set resistant gel,shear resistant gel, sherpa fleece gel construction, shock absorbinggel, silk gel, skin like gel, skin protective gel, slippery gel, softgel, sound barrier gel, spandex gel construction, sponge gel, sportsgel, spun fleece gel construction, stretch gel, sun block gel, tackygel, tear resistant gel, teflon gel, time delay gel, tooth paste flossgel, tracking gel, transfer gel, tri-layer composite gel, vibrationdampening gel, water gel, water gel projectile, water jet control gel,wool gel, and wrinkle gel.

The gel articles molded from the instant compositions have variousadditional important advantages in that they do not crack, creep, tear,crack, or rupture in flexural, tension, compression, or other deformingconditions of normal use; but rather the molded articles made from theinstant composition possess the intrinsic properties of elastic memoryenabling the articles to recover and retain its original molded shapeafter many extreme deformation cycles.

The instant compositions can be formed in any shape; the original shapecan be deformed into another shape (to contact a regular or irregularsurface) by pressure and upon removal of the applied pressure, thecomposition in the deformed shape will recover back to its originalshape.

The invention gels can be made into useful gel articles having no needfor a protective covering, but a protective covering may be use asrequired. Such interlocking with many different materials produce gelcomposites having many additional uses. The high tear resistant softinvention gels made from SEEPS and CD block copolymer gels areadvantageously suitable for a safer impact deployable air bag cushionsas disclosed in my patent Pat. No. 6,627,275 and my application U.S.Ser. No. 10/675,509.

The fishing terms used herein are defined in my copending fishing baitapplications incorporated by reference above. Almost all fish love livefish. The big fish likes to eat smaller fish and other natural lookingprey, such as baitfish, boodworm, caddis, casters, cheese, crayfish,cricket, cut bait fish eggs, fish larvae, frogs, grub, guppies, insects,lizards, lobworm, maggots, mayflies, mealworms, minnows, night-crawler,nymphs, redworm, reptiles, salamanders, shad, shrimp, sinks, slugs,small fishes, snakes, squid, swordtails, water dog, other worms, and thelike.

Fishing baits made from the invention gels may have one or more built-inrattles or pre-formed cavity connected by a channel for later insertionof a rattle for trigger which are conventionally use with PVC softplastic baits. Since the molten temperature of the invention is muchhigher than required to melt PVC plastisol, rattles must be contained ina heat resistant (above about 275° F. to about 450° F.) enclosure formolding into the invention gel bait or the rattles can be glue onto theinvention gel bait with glues described below. When molded into theinvention gel bait, the rattle can be removed by inserting a sewingneedle (the sharp point of a fishing hook, a thumb tack tip of a wire,or any sharp point) through the gel into the region of the rattle. A pinhole can also be molded by using a fine wire with the rattle in place toavoid having to push a needle through the gel. This is called the“rattle through a pin hole method” or “pin hole method”. The rattle canthen be forced or pushed out through the pin hole path made by theneedle. Because of the invention gel is tear resistant, the pin hole canbe enlarged without tearing. The pin hole method does not require aconnecting channel to a pre-formed cavity which promotes drag in thewater. On the small side of the fishing bait any cavity or connectingchannel can promote a great amount of drag. Any undesirable drag willaffect the performance of the fishing bail. The same rattle or a largerrattle can be reinserted any time as desired or any liquid substance(such as a fish attractant, e.g., fish oil and the like) can be injectedin the rattde's place. Multiple pin holes can be made in the inventiongel bait as desired with out affecting the use of the gel bait. A lowtemperature rattle can also be use with the fishing bait by firstmolding the fishing bait with a similar shaped temperature resistantblank, later removed through a pin hole and the desired rattle insertedin place.

The invention baits are suitable for catching all types of freshwaterfish such as: lampreys, bony fishes, sturgeons, paddlefishes, gars,perch, pike, muskellunge, walleye, white bass, pickerel, carp, all typesof bass (small mouth bass, yellow bass, and the like) catfish, bullhead,herrings, shads, salmons, trouts, and the like. The live actioninvention gel fishing baits can last more than five times longer withoutdamage and replace completely the used of conventional PVC plastisolfishing baits which have been determined to contain controversial toxicplasticizers and banned by JAFTMA and certain European countries.

The invention gel fishing baits are about the best to live food, sincethey can be made soft, they move fast and are extremely slippery in thewater and have the motion very much like live prey. The invention gelfishing baits can not only exhibit action, but are capable of exhibitingbuoyancy in water, and can be made to have low tack or be non-tacky tothe touch. The invention gel fishing baits are rupture resistant todynamic stretching, shearing, resistant to ball-up during casting,resistant to tearing encountered during hook penetration, and casting.Therefore, the invention gel fishing baits can be use to catch fish inall manner of presentations of bait, hook, and line combinationsincluding with barbed hooks, barbless hooks bent hooks rig, carolinarig, when critically balanced baiting, dropshot rig, eyed hook,fancasting, finesse fishing, flipping, floating (float fishing), floridarig, jerk bait, jig, jig-n-pig, offset hook, paternoster rig, peggedtexas rig, pro-jo rig, round-bend hook, split shot rig, strike zone,swimming lure, texas rigged worms, tight-action plug, trailer hook,unpegged texas rig, wacky rig, weightless rig, worming and the like. Theinvention gel fishing bait exhibits five times greater elongation,greater tear resistance, and greater fatigue resistance than aconventional plastisol polyvinyl chloride fishing bait of correspondingrigidity.

As a consequence, the invention gel fishing baits are a boon to theangler giving him a success hook to catch ratio of at least greater than5 in side by side fishing with a conventional plastisol PVC bait.Thereby, increasing his catch per unit of effort, increasing his fishingeffectiveness, minimizing his fishing effort of presentation andmaximizing his success. Foods and food components of all types can beincorporated into the invention gels fishing baits to increase catchsuccess. The invention gels are especially suitable and have uses whereimprovements to resistance to dynamic stretching, shearing and tearingforces are particularly needed such as those when forces acting duringfishing as described above and uses as dental flossing disclosed in mypatent Pat. No. 6,161,555, brushing 10/613,567, fishing baitsapplications: 10/199,361, 10/199,362, 10/199,363 and 10/199,364; healthcare: 10/420,489, and tear resistant articles: 10/746,196. Other usesinclude those disclosed in my applications for air bag, liner, divingsuit and muscle 10/675,509, 10/420,492, 10/40,488, and 10/273,828respectively.

In the case of dental flossing, freeze dried dental paste can also beincorporated into the gel and formed into dental floss by passingcoating the dental floss surface with flavors or other agents. Not onlyis the dental floss a floss, it is an effective tooth brush in betweenthe tooth gap between making it a floss-brush with activated tooth pastbuild in. The gel compounded with toothpaste can contain any anticavityagents including sodium fluoride, any anti gingivitis agents, anywhitening agents, and any plaque fighting agents. Freeze dry or powderscontaining hydrated silica, sorbitol, PVM/MA copolymer, sodium laurylsulfate, flavor, sodium hydroxide, triclosan, monoammonium phosphate,calcium sulfate, ammonium chloride, magnesium chloride, methylparaben,propylparaben, coloring, and the like can be compounding into the gelcomposition forming a floss-brush gel composition.

Gel floss formed from the invention gels has many advantages overconventional dental floss such as regular and extra fine waxed andunwaxed nylon floss, spongy nylon fiber floss, and waxed and unwaxedexpanded and unexpended teflon floss. Such conventional floss are notrecommended for use by children, since a slip or sudden snap in forcingthe floss between the teeth may cause injury to the gums which oftentimes results in bleeding. For sensitive gums and inflamed gums whichhas become red and puffy, it is difficult to floss at, near, and belowthe gumline. The soft gel floss with softness substantially matching thesoftness of the gums are of great advantage for use by children and forflossing teeth surrounded by sensitive and tender gums.

The most surprising, unexpected, versatile use of the composition isdental flossing because a long strand of gel floss is difficult tomanage, novel floss designs are shown in FIGS. 5 a-5 m which are userfriendly and can be operated using two opposing fingers or thumbs. Thedental floss can be almost any shape so long as it is suitable fordental flossing. A thick shaped piece of the composition can bestretched into a thin shape and used for flossing. A thinner shapedpiece would require less stretching, etc. For purposes of dentalflossing while flossing between two closely adjacent teeth, especiallybetween two adjacent teeth with substantial contact points and moreespecially between two adjacent teeth with substantial amalgam alloymetal contact points showing no gap between the teeth, it is criticalthat the gel resist tearing, shearing, and crazing while being stretchedto a high degree in such situations. For example, dental gel floss cantake the form of a disk where the segments of the circumference of thedisk is stretched for flossing between the teeth. Other shaped articlessuitable for flossing include threads, strips, yarns, tapes, etc.,mentioned above.

In order for invention gels to be useful as a dental floss, it mustovercome the difficult barriers of high shearing and high tearing underextreme elongation and tension loads. The difficulties that theinvention gels must overcome during flossing can be viewed as follows:during the action of flossing, the gel is stretched from no less thanabout 200% to about 1,100% or higher, the gel floss is deformed as it ispulled down with tearing action between the contacting surfaces of theteeth, then, the wedge of gel floss is sheared between the innercontacting surfaces of the teeth, and finally, the elongated wedged ofgel floss is pulled upwards and out between the surfaces of the teethThe forces encountered in the act of flossing are: tension, shearing,tearing under extreme tension. This invention advances the flossing artby providing strong, soft and extreme tear resistant invention gels madefrom multiblock copolymers which invention gels are substantially assoft as the gums surrounding the teeth.

The invention gels can also be formed directly into articles or remeltedin any suitable hot melt applicator and extruded into shaped articlesand films or spun into threads, strips, bands, yarns, or other shapesusing a tubing header, multi-strand header, wire coating header, and thelike. With respect to various shapes and yarn, its size areconventionally measured in denier (grams/9000 meter), tex (grams/1000meter), and gage (1/2.54 cm). Gage, tex, denier can be converted asfollows: tex =denier/9=specific gravity (2135/gage), for rectangularcross section, tex =specific gravity·(5806×103)(th)(w)/9, where th isthe thickness and w the width of the strip, both in centimeters. Generaldescriptions of (1) block copolymers, (2) elastomeric fibers andconventional (3) gels are found in volume 2, starting at pp. 324415,volume 6, pp 733-755, and volume 7, pp. 515 of ENCYCLOPEDIA OF POLYMERSCIENCE AND ENGINEERING, 1987 which volumes are incorporated herein byreference.

(57) Ford, Jr., in U.S. Pat. No. 5,659,895 teaches a multi-componentfull-body stress transfer suit for eliminating the need for exercise.The suit can be difficult to use in practice on Earth and even more sofor use in outer space in a zero gravity environment. This is becausethe Ford suit is made up of a mesh-like structure system of multiplecomponents such as pads, zippers, cuffs, straps, gloves, flexures,briefs, belts, loops, anchors, rubber strands, and the like. Many of thecomponents, such as the pads and flexures are made of non-stretchmaterials, such as cotton. Every component has to be anchored to anothercomponent for the multi-component rubber strand mesh-like structuresystem to function and not without some difficulty. Moreover, the rubberstrands, cuffs, straps, and belts all can cause chafing of the skin. Thesmaller the components, the greater the potential for greater chaffing.In order to prevent chaffing the skin must be protected from thecomponents. Not only must the skin be protected, the space ship's innerworking parts, equipment and gear must also be protected from the unsafeentanglement prone components of the suit. More difficult is the matterof untangling the suit from itself when moving it or unpacking it fromstorage and there is entanglement dangers when donning it on the body orwhile nudging the body parts into it. A rather difficult to work withmechanical system of interlaced rubber strands or rubber bandsmechanically connected, secured to non-stretchable pads, zippers, cuffs,straps, gloves, flexures, briefs, belts, loops, and anchors. This iswhy, the Ford suit is for maintaining a static load on the body whichsuit is designed for the purpose (in Ford's words) of “eliminating theneed for exercise.” The cuffs at the wrists and ankles would make aperson feel very much like a prisoner and the cage of interlaced rubberstrands would make a person feel much like being confinement in astraight jacket or prison.

(58) In general, Robert Douglas Bruce III in his paper “The Problem ofBone Loss During Space Flight and the Need For more Effective TreatmentsTo Make A Mission to Mars Safer”, of May 28, 2002 available on theinternet, writes: scientist [are] particularly worried . . . [of] therapid loss of bone density experienced by astronauts as a result of thezero gravity conditions in space. Mechanical stimulation in the form ofphysical exercise . . . has little affect on the rate of bone loss . . .extended interplanetary space travel remains too unsafe. The problem ofbone loss during space flight remains, in many ways, a mystery . . . Whyexactly this happens still has researches baffed. Is the mechanicalsignal of gravity somehow converted to a chemical signal (ie. a hormone)that then regulates bone growth? . . . to what extent would the rapidrates of degradation continue? . . .

The loss of bone in space does not affect the entire body (some boneshave actually been shown to gain bone during space flight). The bonessubject to degradation experience the most pressure from the downwardpull of gravity and are known as the “load-bearing” bones of the body.These include ankles, tibia, fomoral neck and greater trochanter, thepelvis, and the lower lumbar vertebrate (Buckey p.28). Though they areunsure exactly why, researchers know that it is the pressure exerted onthese bones by gravity in everyday activity that maintains bone density.Exercise subjecting these bones to strong stresses (ex. weight liftingand running) has been shown to actually increase bone density inathletes [on Earth]. In the zero-gravity conditions of space flight,however, these bones experience rapid depletion and calcium loss.

Another problem . . . is that zero g conditions cause a great decreasein blood pressure to the legs. The presence of gravity on Earth createsa pressure gradient in the body by pulling blood down into the legs. Inzero g conditions, this pressure gradient no longer exists causing bloodto leave the legs and pool more in the torso and upper body regions. Thedecreased blood in the legs makes it extremely difficult to heal/buildup bones in space if they are getting a much smaller blood supply thanthey would be on Earth.

Bone begins to deteriorate shortly after astronauts enter space . . .bone loss occurs at rates of up to one and two percent per month (6-24%per year) in load bearing bones. This is as many as 6 times greater thanthe rate of bone loss of women with severe osteoporosis . . . Somestudies has shown that over extended periods of time, this rate ofdegradation could lead to an overall loss of 40-60% of bone mass inload-bearing bones (Miller p.1) . . . bone degradation puts astronautsat risk of suffering fractures . . . far from Earth . . . an accidentcould mean death for an injured astronaut.

One possible way to combat the lack of gravity . . . would be to spinthe spacecraft . . . [to] create an artificial gravity environment . . .would require certain structural changes . . . to prevent equipmentdamage. Also, though the spin gives some weight to the astronauts itonly provides a fraction of the pull of the Earth's gravity . . . but itwould hardly be enough . . . exercises do reduce the rate of bone lossto a degree, mechanical devices created to simulate this heavy loading[on the heel, leg, and thigh bones] have met with limited success.

A number of different mechanical devices have been developed to simulatethe Earth's gravity during spaceflight. These generally consist of avariety of straps cords and elastic devices to provide load on the legs,hips, and lower back of astronauts . . . Though these exercise machineshave had some effect in battling muscle loss caused during space flight,success has been hindered for a number of reasons. One problem is thefact that the machines often cannot supply sufficient load to theastronauts . . . and the “Russian treadmill”. . . is so uncomfortable .. .

In studies done on Earth, placing large strains on the skeletal systemcan, in some cases, have a negative effect on the skeletal system. Whileexercise generally increases bone density, too much exercise and loadbearing can cause a decrease in bone density. Young women who exercisetoo heavily sometimes experience a decrease in spinal density.Similarly, a study in which a static load was applied to the ulnae ofrats for ten minutes per day showed growth and decreased density (Eismanp.2) . . .

Most likely what will evolve is a combination of drug therapy, physicalexercise, and vibration treatment . . . to greatly reduce the danger tothe astronauts. Until an effective treatment . . . can be found,however, the risk of injury or death is too great to astronauts to meritsending them into space for long periods of time.”

These and many others problems are solved by the present invention.First, our everyday observation teaches us that a large drop of waterwhen dropped from a given height above the surface of the Earth willfall straight down and most likely will deform and may even break upinto smaller droplets along its path. Our intuition tells us that anidentical large drop of water experiencing linear acceleration in outerspace might also deform and break up along its path of acceleration.When the force of acceleration is equal to the force of gravity onEarth, then that large drop of water will break up the same way as itsidentical twin water drop did falling to Earth. The identical twin largedrops of water, if they have the intelligence to determine bymeasurements each of its own force experience, one of gravity on Earthand the other of acceleration in outer space. If they have theopportunity to compare their measurements, they will not be able todiscern any difference, provided, of course, we make sure the pressurearound that large drop of water in outer space is surrounded by the sameone atmosphere of pressure as the water drop is accustom to here onEarth.

The equivalence of the gravitation force, say, on Earth of one G to anequal accelerating force of one G in outer space was first recognized byAlbert Einstein which he called the Equivalence Principle and forms thesecond postulate of his theory, published in 1916. We apply it here.

If a living bone cell structure or living muscle tissue can be slightlydeformed or stressed under a force equivalent to one G (gravitationalforce of the Earth), by using, say, electromagnetic or a dipo-dipoforces, or an elastic force locally, the living bone cell or livingmuscle tissue would not know the the nature of that force, be itgravitational or elastic, electromagnetic, or dipo-dipo forces. So longas it is done carefully. By the use of the elastic forces which aremolecular forces and which are inherently electromagnetic forces of theouter electrons of the atoms making up the molecules, it is possible tocreate an environment that can simulate greater and greater amounts ofequivalent G forces up to the breaking, tearing, or yielding forcesrequired to destroy a elastomeric material. The elastic forces can beviewed as an antagonist that contracts with and limits the action of anagonist with which it is paired. The elastic force can be use toantagonize, can be use antagonistically to act on living cells, livingbone cells, tissue, and bone, and can be use to cause modification toliving systems similar to the action of gravity.

Therefore, theory notwithstanding, this invention set forth conjecturesapplicable to the local domain of living bones and muscle tissue orcells as well as to their aggregate systems of living bones connected toliving, functional muscles tissue within the human body and a body ingeneral. First an elastic force applied to a system locally isequivalent to a gravitational force of the same magnitude applied to thesame system locally. A corollary of this is that Gravity and elasticforces when applied locally to a system can be treated asindistinguishable. Second, an electromagnetic force applied to a systemlocally is equivalent to a gravitational force of the same magnitudeapplied to the same system locally. A corollary to this is that Gravityand electromagnetic forces when applied locally to a system can betreated as indistinguishable.

For example, two conductors having the same direction of high directcurrent electron flow when brought in close proximity will attract eachother. Using high current flow to produce an attraction force equal tothe gravitational force would not be practical, but theelectron-electron force holding the molecule of an elastomeric materialtogether can provide such an equivalent gravitational force. The presentinvention is a dynamic elastomeric body-exercising-suit which hasessentially no non-stretch parts, no skin abrasion parts, and nointerlacing parts that can catch and tangle with equipment. The dynamicelastomeric body-exercising-suit can be made without pads, without theneed for zippers, without cuffs, without straps, without flexures,without briefs, belts, without loops, without anchors, and without theneed for rubber strands.

It is well known that rubber when stretched gives off heat and coolswhen contracted. A rubber band upon extension goes from a lower to ahigher level of order and alignment of the rubber molecules. Its entropydecreases when work is applied to stretch it and heat is given off. Itincreases in entropy when released reverting back into a state ofincreased entropy. A rubber strand or band pressed next to the skin whenstretched can be very uncomfortable due to accompany stretching of theunderlying skin by a high friction rubber surface. When the rubberstrand is released next to the skin, it is even more uncomfortable dueto surface bunching of the underlying skin. This is an inherent problemfor the use of the Ford rubber strand suit and unacceptable to the user.One aspect of the invention utilizes one or more tear resistantelastomers and tear resistant elastomer gels for forming the bodyexercising-suits, swim exercising suits. The tear resistantbody-exercising suits can have a selected thickness covering differentareas of the body.

Friction, drag and resistance are due to motion between surfaces, nomatter how smooth. Even abrasive surfaces can become slippery when wet.In general most surfaces are slippery when wet for example, tiretraction is drastically reduce on a rain soak highway as opposed to whenthe road is dry and the maximum coefficient of friction is realized (atthe point, line, or surfaces which is normal to the weight or force)where the tire meets the road.

In the case of hydroplaning, the tire and road is separated by a layerof water where the tire and road surface is no longer in contact. Aseparating layer of water also occurs between the bottom of a sled whenpulled over the surface of new fallen snow or as the sled bottom isdragged over hard padded snow.

The invention gels can be use on the bottoms of snow skis, snow boards,boards used on snow mobiles, dog sleds, and etc. The invention gels canprovide improved reduction in friction and improve control and speedthan waxes. The invention gels can provide smoother and better controlof skies than fluorinated waxes and fluorinated hydrocarbon coatings.The invention gels can reduce or eliminate mechanical wear, reduceabrasion of the ski base surfaces, and reduce the formation of finehairs of damage ski base materials in the temperature range of from lessthan 5° F. to 15° F. and higher. The invention gels can improve sliding.The invention gels can be patterned or contoured for climbing, and forgripping the snow without the problem of generating noise or vibrations,because the invention gel acts as a noise and vibration damper as well.The invention gels are excellent in dry, granular, wet snow, and icingconditions. The invention gels can be compounded with salts so as toproduce a very thin water layer at the snow-gel, or ice-gel interface.

The invention gels are excellent as a anti fouling layer for oceanvessels hulls, for pipe liner allowing a pig to move freely and inslippery motion. The invention gels are slippery in water and do notpromote organic or protein adhesion or built-up by oceanospirillum,barnacle, other crusty fouler, and the like. It dampens noise,vibrations, shock, and is hydrophilic. It prevents or reduces cavitationin water by absorbing energy and is in some degree in motion with thewater retarding the production of air bubbles. The invention gels isnon-toxic and can reduce drag and friction allowing submerged vessels tomove faster in water requiring less energy. The invention gels whenincorporated as a outer layer of a submerged vessel is much like thesleek, smooth dolphin skin. The invention gels is much like amaintenance free coating of gelatinous fat able to withstand extremepressures and temperatures of the ocean depths. Such invention gelswould be ideal for use as a thin coating on the USN's Undersea Glider orthe OED's Seaglider roaming the seas for maintenance free oceanographywork, reconnaissance, communications, sea floor bottom profiling, andnavigation aids. One of the main problems with the Seaglider ispotential fouling according to Russ light with the Ocean EngineeringDepartment of the Applied Physics laboratory. The Seaglider has noexternal moving parts and can reach a depths up to 1000 meters, andcovering 6000 kilometers on a single charge.

The invention gels are prepared by blending together the components (I,II, or III) including the various additives as desired at about 23° C.to about 100° C. forming a paste like mixture and further heating saidmixture uniformly to about 150° C. to about 200° C. until a homogeneousmolten blend is obtained. Lower and higher temperatures can also beutilized depending on the viscosity of the oils and amounts ofmultiblock copolymers and polymer (III) used. These components blendeasily in the melt and a heated vessel equipped with a stirrer is allthat is required. Small batches can be easily blended in a test tubeusing a glass stirring rod for mixing. While conventional large vesselswith pressure and/or vacuum means can be utilized in forming largebatches of the instant compositions in amounts of about 40 lbs or lessto 10,000 lbs or more. For example, in a large vessel, inert gases canbe employed for removing the composition from a closed vessel at the endof mixing and a partial vacuum can be applied to remove any entrappedbubbles. Stirring rates utilized for large batches can range from aboutless than 10 rpm to about 40 rpm or higher.

The invention gel can also contain gases as an additive, i.e. the gelcan be foamed. Foam is herein defined as tightly or loosely packingaggregation of gas bubbles, separated from each other by thin or thicklayers of gel. Many types of foamed invention gels (from ultra highdensity to ultra low density) can be produced as desired by adding gasto the molten gel during processing, and producing gas in the molten gelduring processing. Gas can be added by whipping a gas into the moltengel before it cools or introduce a gas into the molten gel and thenexpand or reduce the size of the gas bubbles by reducing the pressure toreduce the bubbles size or applying high pressure to expand the bubblessize. In this regard, inert gases such as Carbon dioxide, Nitrogen,Helium, Neon, Argon, Krypton, Xenon and Radon are suitable. Air can alsobe used. Gas can be produced in the molten gel by adding one or more ofa “blowing agent” to the. Useful blowing agents include dinitrosocompounds, such as dinitroso pentamethylene-tetramine, azodicarbonamide,4,4′oxybis (benzenesulfonyl) hydrazine, 5-phenyltetrazole,p-toluenesulfonyl semicarbazide, sulfonyl hydrazide, such as benzenesulfonylhydrazide. Water can be used as a “blowing agent” to producevarying density of foam invention gels; water used to advantage can bein the form of mist, droplets, steam, and hot or cold water. The densityof the foam invention gels can vary from less than 1.00 kilograms percubic meter to near the solid gel density. Although the materialsforming soft solid invention gels may be more shear resistant, the samematerials when made into a foam become much less shear resistant.

The gel articles can be formed by blending, injection molding,extruding, spinning, casting and other conventional methods. Forexample, Shapes having various crossection can be extruded using aHP-2000 Mixing extruder from Dek-tron Scientific Instruments ofPlainfield, N.J. 07060, USA.

EXAMPLES

While advantageous components and formulation ranges based on thedesired properties of the multiblock copolymer invention gels have beendisclosed herein. Persons of skill in the art can extend these rangesusing appropriate material according to the principles discussed herein.All such variations and deviations which rely on the teachings throughwhich the present invention has advanced the art are considered to bewithin the spirit and scope of the present invention. The invention isfurther illustrated by means of the following illustrative embodiments,which are given for purpose of illustration only and are not meant tolimit the invention to the particular components and amounts disclosed.

Example I

Gels of 100 parts of Kraton G1651, Kuraray Septon 2006 (SEPS), KuraraySepton 8006 (SEBS), a high viscosity (SEB)_(n), and a high viscosity(SEP)_(n) triblock copolymers and 1,600, 1,200, 1,000, 800, 600, 500,450, and 300 parts by weight of Duraprime 200 white oil are melt blendedand samples extruded (from a 7.15 mm diameter orifice) into selectedlengths of varying diameters for use as dental floss, the bulk gelrigidities is found to be within the range of 2 to 1,800 gram Bloom, thetensile strength is found to decrease with increase orientation, and theoptimum tensile strength found for gel samples with the least amount ofstress or orientation imparted during cool from the molten state to roomtemperature.

Example II

Example I is repeated using Kuraray (S-E-EP-S) 4055 and 4077 multiblockcopolymers, the bulk gel rigidities are found to be within the range of2 gram to 1,800 gram Bloom and the tear resistance of the multiblockcopolymers at corresponding rigidities are found to be substantiallyhigher than the tear resistance of the triblock copolymer gels ofEXAMPLE I. The tensile strength is found to decrease with increaseorientation, and the optimum tensile strength found for gel samples withthe least amount of stress or orientation imparted during cool from themolten state to room temperature.

Example III

Example I is repeated using (S-E-EP-S), (S-E-EP-E-S), (S-B-EP-S),(S-E-EB-S), (S-EB-EP-S), (S-E-EP-EB-S), (S-B-EB-S), (S-E-EB-E-S),(S-B-EP-E-S), (S-B-EB-E-S), (S-B-EP-B-S), (S-B-EB-B-S), (S-E-E-EP-S),(S-E-E-EB-S), (S-B-E-EP-S), (S-B-E-EB-S), (S-B-B-EP-S), (S-B-B-EB-S),(S-E-B-EB-S), (S-E-B-EP-S), (S-EB-EB-S), (S-EP-EP-S), (S-E-EB-EB-S),(S-E-EP-EP-S), (S-E-EB-EP-S), (S-B-EB-EB-S), (S-B-EP-EP-S), (S-E-EP)n,(S-E-EP-E)n, (S-B-EP)n, (S-E-EB-S)n, (S-EB-EP-)n, (S-E-EP-EB)n,(S-B-EB)n, (S-E-EB-E)n, (S-B-EP-E)n, (S-B-EB-E)n, (S-B-EP-B)n,(S-B-EB-B)n, (S-E-E-EP)n, (S-E-E-EB)n, (S-B-E-EP)n, (S-B-E-EB)n,(S-B-B-EP)n, (S-B-B-EB)n, (S-E-B-EB)n, (S-E-B-EP)n, (S-EB-EB)n,(S-EP-EP)n, (S-E-EB-EB)n, (S-E-EP-EP)n, (S-E-EB-EP)n, (S-B-EB-EB)n,(S-B-EP-EP)n, (S-B-EB-EP)n, (S-B-EP-EB)n, (S-E-EP-E-EP)n, (S-E-EB-E-EB)nmultiblock copolymers, the bulk gel rigidities are found to be withinthe range of 2 gram to 1,800 gram Bloom and the tear resistance of themultiblock copolymers at corresponding rigidities are found to besubstantially higher than the tear resistance of the triblock copolymergels of EXAMPLE I. The tensile strength is found to decrease withincrease orientation, and the optimum tensile strength found for gelsamples with the least amount of stress or orientation imparted duringcool from the molten state to room temperature.

Example IV

Example II is repeated using plasticizers L-14, L-50, L-100, H-15, H-25,H-35, H-50, H-100, H-300, L-14E, H-300E, Actipol E6, E16, E23, KratonL-1203, EKP-206, EKP-207, HPVM-2203, Amoco C-60, Piccolyte S10,Duraprime (55, 70, 90, 200, 350, 400), Tufflo (6006, 6016, 6016M, 6026,6036, 6056, 6206) Bayol, Bemol, American, Blandol, Drakeol, Ervol,Gloria, and Kaydol, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the tear resistance of themultiblock copolymers at corresponding rigidities are found to besubstantially higher than the tear resistance of the triblock copolymergels of EXAMPLE I.

Example V

Example III is repeated using plasticizers L-14, L-50, L-100, H-15,H-25, H-35, H-50, H-100, H-300, L-14E, H-300E, Actipol E6, E16, E23,Kraton L-1203, EKP-206, EKP-207, HPVM-2203, Amoco C-60, Piccolyte S10,Duraprime (55, 70, 90, 200, 350, 400), Tufflo (6006, 6016, 6016M, 6026,6036, 6056, 6206) Bayol, Bemol, American, Blandol, Drakeol, Ervol,Gloria, and Kaydol, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the tear resistance of themultiblock copolymers at corresponding rigidities are found to besubstantially higher than the tear resistance of the triblock copolymergels of EXAMPLE I.

Example VI

A gel composition of 100 parts of Kuraray's S-E-EP-S 4055 copolymer and400 parts by weight of Duraprime 200 white oil was made followingExample I and extruded and drawn (from a 7.15 mm diameter orifice) intoa strand of uniform diameter onto a take-up roll of continuous lengths.The strand diameter was varied by increasing and decreasing the speed ofthe take-up roll. The continuous strand of varying diameter gel strandwas cut to suitable lengths for use and testing as dental floss.Additional gel was also casted in varying thickness and tested Theresults of samples tested are shown in Table 3, #4-7; Table 4, #12-15and 20; Table 5 #22, 23, 27-29; Table 6 #36-32; Table 7, #40-43, #76 and77. Sample Nos. 76 and 77 were tested together. Sample 77 exhibitedhigher tensile strength after 27.75% of plasticizing oil was extracted(with 2.89 parts by weight of oil remaining), its rigidity remainedsubstantially unchanged.

Example VII

A gel composition of 100 parts of Kraton G1651 and 400 parts by weightof Duraprime 200 white oil was made following Example I and extruded anddrawn (from a 7.15 mm diameter orifice) into a strand of uniformdiameter onto a take-up roll of continuous lengths. The strand diameterwas varied by increasing and decreasing the speed of the take-up roll.The continuous strand of varying diameter gel strand was cut to suitablelengths for use and testing as dental floss. Additional gel was alsocasted in varying thickness and tested. The results of samples testedare shown in Table 3B, #8-11; Table 4, #16-19 and 21; Table 5, #2426;Table 6, #33-35; and Table 7, #36-39.

Example VIII

Example II was repeated melt blending under inert gas 100 parts byweight of Kuraray (S-E-EP-S) 4077 multiblock copolymer and 400 parts byweight of Duraprime 70 white oil. A first part of the molten gel wasallowed to cool to room temperature, the remainder gel was heated underinert gas for an additional three hours at 300-325° F. and a second partof the gel was extruded (from a 7.15 mm diameter orifice) into coldrunning water, and the third and final remaining gel was allowed to coolto room temperature. The bulk gel rigidities of the first second andthird parts were found to be within the range of 2 to 1,800 gram Bloom.The second and third final parts of the gel appeared to be altered anddifferent from the first gel part. The first part exhibited rapid returnwhen extended, but the second and third final parts exhibited delayelastomeric recovery when released after extension and deformation. Allof the samples exhibited 100% recovery after repeated extensions anddeformations.

The tensile strengths of invention gels made from higher viscositycopolymers are lower than the tensile strengths of gels made from lowersolution viscosity copolymers. This was later found to be due toorientation effects and not considered significant.

The tear resistance of invention gels made from higher viscositycopolymers are higher than the tear resistance of invention gels madefrom lower solution viscosity copolymers.

Gel strands made from higher viscosity copolymers perform better thangel strands made of lower viscosity copolymers when used in flossingamalgam molars and more than three times better when used in flossingfront teeth.

As compared to spongy nylon, regular waxed nylon, and extra fine unwaxednylon when flossing amalgam molars, the performance of invention gelsare on the average substantially better.

Examples below illustrate other modes of practice contemplated.

Example IX

At least 120 pcs of the gel strands of EXAMPLE II containing 600 partsoil is individually weighted and placed in a heated vacuum oven, apartial vacuum is applied and the temperature is regulated between about80° F. to about 150° F. to extract plasticizer from the gel strands. Atvarious oven and vacuum times, three gel strands are removed from thevacuum oven, allowed to cool to room temperature, weighted to determinethe amount of weight loss and tested for tensile and tear strength. Asthe amount of oil contained in the original gel is reduced from 600parts by weight to less than 200 parts by weight, the “reducedplasticizer volume” invention gels are weighted and tested. The tear andtensile strengths of the reduced plasticizer volume invention gels arefound to be improved over the properties of the original 600 parts byweight referenced gel strands.

The invention gels are especially advantageously useful when subjectedto conditions of stretching, shearing, and tearing during flossing. Theinvention gels useful for flossing are characterized by low rigiditiesand high solution viscosity of the invention gels made from multiblockcopolymers having two or more midblock polymer chains.

Example X

Gels of 100 parts of Kraton G1651, Kraton RP-6917 (amorphous S-EB-S),Septon 8006 (amorphous S-EB-S), Kraton RP-6918, Septon S2006 (amorphousS-EP-S) and a high viscosity radial amorphous midblock segment (SEB)_(n)triblock copolymers and 1,600, 1,200, 1,000, 800, 600, 500, 450, 300,250 parts by weight of Duraprime 200 white oil (plasticizer having Vis.cSt @ 40° C. of 39.0) are melt blended, test, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2 to1,800 gram Bloom and the tensile strength, notched tear strength, andresistance to fatigue are found to decrease with increase amounts ofplasticizers, while tackiness of the gels is found to be greater than7.6 gram Tack.

Example XI

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 and 1,600, 1,200, 1,000, 800, 600, 500, 450, 300, 250 parts byweight of Duraprime 200 white oil (plasticizer having Vis. cSt @ 40° C.of 39.0) are melt blended, test and tack probe samples molded, the bulkgel rigidities are found to be within the range of 2 to 1,800 gram Bloomand the gel tackiness are found to increase with increase amounts ofplasticizers and the tack greater than 7.6 gram Tack.

Example XII

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow S seriespoly(ethylene/styrene) random copolymer (250,000 Mw) having a highstyrene content sufficient to form gel blends with total styrene contentof 37 by weight of copolymers and 800, 600, 500, 450, 300, 250 parts byweight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20)are melt blended, tests, and tack probe samples molded, the bulk gelrigidities are found to be within the range of 2 gram to 1,800 gramBloom and the notched tear strength and resistance to fatigue of the gelat corresponding rigidities are found to be greater than that ofamorphous gels of Example I, while tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

Example XIII

Gels of 100 parts of Septon 4045 (crystalline S-EIEP-S having a styrenecontent of 37.6) and 1,600, 1,200, 1,000, 800, 600, 500, 450, 300, 250parts by weight of Duraprime Klearol white oil (plasticizer having Vis.CSt @ 40° C. of 7-10) are melt blended, test and probe samples molded,the bulk gel rigidities are found to be within the range of 2 to 2,000gram Bloom and the tackiness is found to be less than about 1 gram Tack.

Example XIV

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of Septon 2104(Amorphous SEPS having a high styrene content of 65) and 800, 600, 500,450, 300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example X and XI.

Example XV

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow M seriespoly(ethylene/styrene) random copolymer (350,000 Mw) having a highstyrene content sufficient to form gel blends with total styrene contentof 37 by weight of copolymers and 800, 600, 500, 450, 300, 250 parts byweight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol, Semtol85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20)are melt blended, tests, and tack probe samples molded, the bulk gelrigidities are found to be within the range of 2 gram to 1,800 gramBloom and the notched tear strength and resistance to fatigue of the gelat corresponding rigidities are found to be greater than that ofamorphous gels of Example I, while tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

Example XVI

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow E seriespoly(ethylene/styrene) random copolymer (240,000 Mw) having a highstyrene content sufficient to form gel blends with total styrene contentof 37 by weight of copolymers and 800, 600, 500, 450, 300, 250 parts byweight of Duraprime 55, 70, Klearol, Camation, Blandol, Benol, Semtol85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of less than 20)are melt blended, tests, and tack probe samples molded, the bulk gelrigidities are found to be within the range of 2 gram to 1,800 gramBloom and the notched tear strength and resistance to fatigue of the gelat corresponding rigidities are found to be greater than that ofamorphous gels of Example I, while tack is found to decrease withdecreasing plasticizer content and in all instances substantially lowerthan the gels of Example I and II.

Example XVII

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with polystyrene homopolymers (having Mw of3,000; 4,000; 5,000; 6,000; 7,000; 8,000; 9,000; 10,000; 11,000; 12,000,13,000; 14,000; 15,000; 16,000; 17,000; 18,000; 19,000; 20,000; 30,000;40,000; 50,000; 60,000; 70,000; 80,000; 90,000) in sufficient amounts toform gel blends with total styrene content of 37, 45, 48, 50, and 55 byweight of copolymers and 800, 600, 500, 450, 300, 250 parts by weight ofDuraprime 55, 70, Klearol, Camation, Blandol, Benol, Semtol 85, 70, and40 (plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 2,000 gram Bloom and tackis found to decrease with decreasing plasticizer content and in allinstances substantially lower than the gels of Example I and II.

Example XVIII

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow M seriespoly(ethylene/styrene) random copolymer (350,000 Mw) having a highstyrene content sufficient to form gel blends with total styrenecontents of 40, 45, 48, 50, and 55 by weight of copolymers and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I, while tack isfound to decrease with decreasing plasticizer content and in allinstances substantially lower than the gels of Example I and II.

Example XIX

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow S seriespoly(ethylene/styrene) random copolymers (with Mw of 140,000; 250,000and 340,000) having a high styrene content sufficient to form gel blendswith total styrene content of 40, 45, 48, 50, and 55 by weight ofcopolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

Example XX

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow E seriespoly(ethylene/styrene) random copolymers (with Mw of 250,000; 340,000and 400,000) having a high styrene content sufficient to form gel blendswith total styrene content of 40, 45, 48, 50, and 55 by weight ofcopolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

Example XXI

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dow M seriespoly(ethylene/styrene) random copolymer (with Mw of 250,000; 340,000 and400,000) having a high styrene content sufficient to form gel blendswith total styrene content of 40, 45, 48, 50, and 55 by weight ofcopolymers and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example I, while tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and II.

Example XXII

Gels of 100 parts of Dow E series crystalline poly(ethylenelstyrene)random copolymer (with Mw of 250,000; 340,000 and 400,000) having a highstyrene content sufficient to form gel blends with total styrene contentof 37, 40, 45, 48, 50, 55, and 60 by weight of copolymers and 800, 600,500, 450, 300, 250 parts by weight of Duraprime 55, 70, Kearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example I, while tack isfound to decrease with decreasing plasticizer content and in allinstances substantially lower than the gels of Example I and II.

Example XXIII

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with polystyrene (of 2,500 Mw, 4,000 Mw, 13,000Mw, 20,000 Mw, 35,000 Mw, 50,000 Mw, and 90,000 Mw;poly(alpha-methylstyrene) (of 1,300 Mw, 4,000 Mw;poly(4-methylstyrene)(of 72,000 Mw), Endex 155, 160, Kristalex 120, and140) in sufficient amounts to form gel blends with total styrene contentof 37, 45, 48, 50, and 55 by weight of copolymers and 800, 600, 500,450, 300, 250 parts by weight of Duraprime 55, 70, Klearol, Camation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 2,000 gram Bloom and tack is found to decrease with decreasingplasticizer content and in all instances substantially lower than thegels of Example I and 11.

Example XXIV

Examples XIV is repeated and gels of 100 parts of (S-EB45-EP-S),(S-E-EB25-S), (S-EP-E-EP-S), (S-E-EB-S), (S-E-EP-S), (S-E-EP-E-S),(S-E-EP-EB-S), (S-E-EP-E-EP-S). (S-E-EP-E-EB-S), (S-E-EP-E-EP-E-S),(S-E-EP-E-EB-S), (S-E-EP-E-EP-EB-S), and (S-E-EP-E-EP-E-S) blockcopolymers are each melt blended, tests and probe samples molded, thebulk gel rigidities are found to be within the range of 2 to 1,800 gramBloom and tack is found to decrease with decreasing plasticizer contentand in all instances substantially lower than the gels of Example I andII.

Example XXV

Example XIV is repeated and minor amounts of 2, 5, 10 and 15 parts ofthe following polymers are formulated with each of the triblockcopolymers: styrene-butadiene-styrene block copolymers,styrene-isoprene-styrene block copolymers, low viscositystyrene-ethylene-butylene-styrene block copolymers,styrene-ethylene-propylene block copolymers,styrene-ethylene-propylene-styrene block copolymers, styrene-butadiene,styrene-isoprene, polyethyleneoxide, poly(dimethylphenylene oxide),polystyrene, polybutylene, polyethylene, polypropylene, high ethylenecontent EPDM, amorphous copolymers based on2,2-bistrifluoromethyl-4,5-difuoro-1,3-dioxole/tetrafluoroethylene. Thebulk gel rigidities of each of the formulations are found to be withinthe range of 2 gram to 2,000 gram Bloom and tack is found to decreasewith decreasing plasticizer content and in all instances substantiallylower than the gels of Example I and 11.

Example XXVI

Molten gels of Examples III-XVI are formed into composites with paper,foam, plastic, elastomers, fabric, metal, concrete, wood, glass,ceramics, synthetic resin, synthetic fibers, and refractory materialsand the resistance to fatigue of the composite-gels at correspondingrigidities are found to be greater than that of the composite-amorphousgels of Example X.

Example XXVII

Three cm thick sheets of each of the gels of Example XIV and theamorphous gels of Example I are tested by repeatedly displacing thesheets to a depth of 1 cm using a 10 cm diameter smooth (water soaked)wood plunger for 1,000, 5,000, 10,000, 25,000, 50,000, and 100,000cycles. The sheets of gels are found capable of exhibiting greaterfatigue resistance than the sheets of amorphous gels at correspondingrigidities.

Example XXVIII

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES16 having 37.5% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Camation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample X.

Example XXIX

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES24 having 26.6% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample X.

Example XXX

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES27 having 17.4% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample X.

Example XXXI

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES28 having 22.9% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample X.

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES30 having 19.6% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Camation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample X.

Example XXXIII

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES44 having 5.0% crystallinityand 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70,Klearol, Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizershaving Vis. CSt @ 40° C. of less than 20) are melt blended, tests, andtack probe samples molded, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom and the notched tearstrength and resistance to fatigue of the gel at correspondingrigidities are found to be greater than that of amorphous gels ofExample X.

Example XXXIV

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES72 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Camation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example X.

Example XXXV

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES73 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Carnation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example X.

Example XXXVI

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES74 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Camation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example X.

Example XXXVII

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES69 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Camation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example X.

Example XXXVIII

Gels of 100 parts of Septon crystalline (SEEPS) copolymers 4033, 4055,and 4077 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES62 and 800, 600, 500, 450,300, 250 parts by weight of Duraprime 55, 70, Klearol, Camation,Blandol, Benol, Semtol 85, 70, and 40 (plasticizers having Vis. CSt @40° C. of less than 20) are melt blended, tests, and tack probe samplesmolded, the bulk gel rigidities are found to be within the range of 2gram to 1,800 gram Bloom and the notched tear strength and resistance tofatigue of the gel at corresponding rigidities are found to be greaterthan that of amorphous gels of Example X.

Example XXXIX

Gels of 100 parts of Septon (SEPS) copolymers Kraton GRP6918 incombination with each of a Dow poly(ethylene/styrene) random copolymersES16, ES24, ES27, ES28, FS30, and ES44 and 800, 600, 500, 450, 300, 250parts by weight of Duraprime 55, 70, Klearol, Carnation, Blandol, Benol,Semtol 85, 70, and 40 (plasticizers having Vis. CSt @ 40° C. of lessthan 20) are melt blended, tests, and tack probe samples molded, thebulk gel rigidities are found to be within the range of 2 gram to 1,800gram Bloom and the notched tear strength and resistance to fatigue ofthe gel at corresponding rigidities are found to be greater than that ofamorphous gels of Example X.

Example XL

Gels of 100 parts of Septon (SEBS) copolymers S8006 and Kraton G1651,G1654 in combination with sufficient amounts of a Dowpoly(ethylene/styrene) random copolymers ES 16. ES24, ES27, ES28, ES30,and ES44 and 800, 600, 500, 450, 300, 250 parts by weight of Duraprime55, 70, Kearol, Camation, Blandol, Benol, Semtol 85, 70, and 40(plasticizers having Vis. CSt @ 40° C. of less than 20) are meltblended, tests, and tack probe samples molded, the bulk gel rigiditiesare found to be within the range of 2 gram to 1,800 gram Bloom and thenotched tear strength and resistance to fatigue of the gel atcorresponding rigidities are found to be greater than that of amorphousgels of Example X.

Example XLI

Gels of 100 parts of Septon (SEEPS) copolymers 4033, 4045, 4055, 4077 incombination each with 25 parts by weight of Super Sta-tac, BetapreneNevtac, Escorez, Hercotac, Wingtack, Piccotac, polyterpene, Zonarez,Nirez, Piccolyte, Sylvatac, glycerol ester of rosin (Foral),pentaerythritol ester of rosin (Pentalyn), saturated alicyclichydrocarbon (Arkon P), coumarone indene (Cumar LX), hydrocarbon (Picco6000, Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035) and 800,600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Carnation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example X.

Example XLII

Gels of 100 parts of Septon (SEEPS) copolymers 4033, 4045, 4055, 4077 incombination each with 25 parts by weight of Super Sta-tac, BetapreneNevtac, Escorez, Hercotac, Wingtack, Piccotac, polyterpene, Zonarez,Nirez, Piccolyte, Sylvatac, glycerol ester of rosin (Foral),pentaerythritol ester of rosin (Pentalyn), saturated alicyclichydrocarbon (Arkon P), coumarone indene (Cumar LX), hydrocarbon (Picco6000, Regalrez), mixed olefin (Wingtack), alkylated aromatic hydrocarbon(Nevchem), Polyalphamethylstyrene/vinyl toluene copolymer (Piccotex),polystyrene (Kristalex, Piccolastic), special resin (LX-1035) and 800,600, 500, 450, 300, 250 parts by weight of Duraprime 55, 70, Klearol,Camation, Blandol, Benol, Semtol 85, 70, and 40 (plasticizers havingVis. CSt @ 40° C. of less than 20) are melt blended, tests, and tackprobe samples molded, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of Example X.

Example XLIII

Gels of 100 parts of (50 parts by weight of Septon (SEEPS) and 50 partsby weight of Kraton 1651) copolymers in combination with 600 parts byweight of (300 parts by weight of Witco 40 oil and 300 parts ofBlandol), 0.05 parts by weight of Irganox 1010, and 0.1 parts by weightof Tinuvin P, are melt blended, tests, and tack probe samples molded,the bulk gel rigidities are found to be within the range of 2 gram to1,800 gram Bloom and the notched tear strength and resistance to fatigueof the gel at corresponding rigidities are found to be greater than thatof amorphous gels of made from Septon 2006 SEPS. The resulting gel isfound to have an elongation greater than 500% and is used to moldfishing baits in the form of a worm, a frog, a lizard, a fish for use ona Carolina Rig, a Texas Rig, and a Wacky Rig presentation and thefishing baits are found to exhibit a success hook to catch ratio greaterthan 5 as compared to a conventional plastisol polyvinyl chloridefishing bait of corresponding rigidity.

Example XLIV

Gels of 100 parts of (50 parts by weight of Septon (SEEPS) and 50 partsby weight of Kraton 1651) copolymers in combination with 600 parts byweight of (300 parts by weight of Witco 40 oil and 300 parts ofBlandol), 0.05 parts by weight of Irganox 1010, and 0.1 parts by weightof Tinuvin P, the bulk gel rigidities are found to be within the rangeof 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of made from Septon 2006 SEPS.The resulting gel is found to have an elongation greater than 800% andis used to mold fishing baits in the form of a worm, a frog, a lizard, afish for use on a Carolina Rig, a Texas Rig, and a Wacky Rigpresentation and the fishing baits are found to exhibit a success hookto catch ratio greater than 5 as compared to a conventional plastisolpolyvinyl chloride fishing bait of corresponding rigidity.

Example XLV

Gels of 100 parts of (50 parts by weight of Septon (SEEPS) and 50 partsby weight of Kraton 1651) copolymers in combination with 600 parts byweight of (300 parts by weight of Witco 40 oil and 300 parts ofBlandol), 0.05 parts by weight of Irganox 1010, and 0.1 parts by weightof Tinuvin P, the bulk gel rigidities are found to be within the rangeof 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of made from Septon 2006 SEPS.The resulting gel is found to have an elongation greater than 900% andis used to mold fishing baits in the form of a worm, a frog, a lizard, afish for use on a Carolina Rig, a Texas Rig, and a Wacky Rigpresentation and the fishing baits are found to exhibit a success hookto catch ratio greater than 5 as compared to a conventional plastisolpolyvinyl chloride fishing bait of corresponding rigidity.

Example XLVI

Gels of 100 parts of (50 parts by weight of Septon (SEEPS) and 50 partsby weight of Kraton 1651) copolymers in combination with 600 parts byweight of (300 parts by weight of Witco 40 oil and 300 parts ofBlandol), 0.05 parts by weight of Irganox 1010, and 0.1 parts by weightof Tinuvin P, the bulk gel rigidities are found to be within the rangeof 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of made from Septon 2006 SEPS.The resulting gel is found to have an elongation greater than 1,000% andis used to mold fishing baits in the form of a worm, a frog, a lizard, afish for use on a Carolina Rig, a Texas Rig, and a Wacky Rigpresentation and the fishing baits are found to exhibit a success hookto catch ratio greater than 5 as compared to a conventional plastisolpolyvinyl chloride fishing bait of corresponding rigidity.

Example XLVII

Gels of 100 parts of (50 parts by weight of Septon (SEEPS) and 50 partsby weight of Kraton 1651) copolymers in combination with 600 parts byweight of about 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and about 14 cSt @ 40°C. viscosity oils, 0.05 parts by weight of Irganox 1010, and 0.1 partsby weight of Tinuvin P, the bulk gel rigidities are found to be withinthe range of 2 gram to 1,800 gram Bloom and the notched tear strengthand resistance to fatigue of the gel at corresponding rigidities arefound to be greater than that of amorphous gels of made from Septon 2006SEPS. The resulting gel is found to have increasing Gram Tack valueswith increasing oil viscosity, increase resistance to heat set at 50° C.as determined under 180° U bend for one hour, an elongation greater than500% and is used to mold fishing baits in the form of a worm, a frog, alizard, a fish for use on a Carolina Rig, a Texas Rig, and a Wacky Rigpresentation and the fishing baits are found to exhibit a success hookto catch ratio greater than 5 as compared to a conventional plastisolpolyvinyl chloride fishing bait of corresponding rigidity.

Example XLVIII

Gels of 100 parts of (50 parts by weight of Septon (SEEPS) and 50 partsby weight of Kraton 1651) copolymers in combination with 600 parts byweight of about 18, 24, 28, 35, 39, 57, 61 and about 64 cSt @ 40° C.viscosity oils, 0.05 parts by weight of Irganox 1010, and 0.1 parts byweight of Tinuvin P, the bulk gel rigidities are found to be within therange of 2 gram to 1,800 gram Bloom and the notched tear strength andresistance to fatigue of the gel at corresponding rigidities are foundto be greater than that of amorphous gels of made from Septon 2006 SEPS.The resulting gel is found to have increasing Gram Tack values withincreasing oil viscosity, increase resistance to heat set at 50° C. asdetermined under 180° U bend for one hour, an elongation greater than500%0 and is used to mold fishing baits in the form of a worm, a frog, alizard, a fish for use on a Carolina Rig, a Texas Rig, and a Wacky Rigpresentation and the fishing baits are found to exhibit a success hookto catch ratio greater than 5 as compared to a conventional plastisolpolyvinyl chloride fishing bait of corresponding rigidity.

Example XLIV

Gel of 100 parts of of Kraton 1651 copolymer in combination with 600parts by weight of (50 parts by weight of Arcro Prime 55 and 50 parts byweight of Arco prime 70), 0.05 parts by weight of Irganox 1010, and 0.1parts by weight of Tinuvin P, the bulk gel rigidities are found to bewithin the range of 2 gram to 1,800 gram Bloom. The resulting gel isfound to have heat set greater than 50° C. as determined under 180′ Ubend for one hour, an elongation greater than 500% and mold in the formof a fishing bait exhibit greater strength than a conventional plastisolpolyvinyl chloride fishing bait of corresponding rigidity.

Example XLV

The following gels were made with 600 parts by weight of oil, 0.5 partsby weight of Irganox 1010, and 0.5 parts by weight of Tinuvin P, meltblended in a 16×150 mm glass test tube, cooled, removed, and 180° U bendtested 50° C. for 1.0 hour.

-   -   1a. 80 parts by weight of Septon 4055 and 20 parts by weight of        Septon 2006, block copolymers, Witco 40 oil, the gel sample        retained a deformation of about 30°.    -   2a. 80 parts by weight of Septon 8006 and 20 parts by weight of        Septon 4055, block copolymers, 35 parts by weight of Endex 160,        Witco 40 oil, the gel heat tested sample retained a deformation        of about 84°.    -   3a. Gels of 90 parts by weight of Septon 8006 and 10 parts by        weight of Septon 4055, block copolymers, 35 parts by weight of        Endex 160, Witco 40 oil, the gel heat tested sample retained a        deformation of about 85°.    -   4a. Gels of 80 parts by weight of Septon 8006 and 20 parts by        weight of Septon 4055, block copolymers, 45 parts by weight of        Endex 160, Witco 40 oil, the gel heat tested sample retained a        deformation of about 91°.    -   5a. Gels of 90 parts by weight of Septon 8006 and 10 parts by        weight of Septon 4055, block copolymers, 45 parts by weight of        Endex 160, Witco 40 oil, the gel heat tested sample retained a        deformation of about 95°.    -   6a. Gels of 100 parts by weight of Septon 8006, block        copolymers, 25 parts by weight of Endex 155, Witco 40 oil, the        gel heat tested sample retained a deformation of about 56°.    -   7a. Gels of 100 parts by weight of Septon 8006, block        copolymers, 45 parts by weight of Endex 155, Witco 40 oil, 0.5        parts by weight of Irganox 1010, the gel heat tested sample        retained a deformation of about 57°.    -   8a. Gels of 100 parts by weight of Septon 4055, block        copolymers, Witco 40 oil, the gel heat tested sample retained a        deformation of about 90°.    -   9a. Gels of 60 parts by weight of Septon 4055 & 30 parts by        weight of Kraton 1651 block copolymers, Witco 40 oil, the gel        heat tested sample retained a deformation of about 45°.    -   10a. Gels of 30 parts by weight of Septon 4055 & 60 parts by        weight of Kraton 1651 block copolymers, Witco 40 oil, the gel        heat tested sample retained a deformation of about 55°.    -   11a. Gels of 100 parts by weight of Septon 8006 block copolymers        in combination with 33 parts by weight of a GE PPO Blendex®        HPP821, 600 parts by weight of Witco 40 oil, the gel heat tested        sample retained a deformation of about 10′.    -   12a. Gels of 60 parts by weight of Septon 4055 & 30 part by        weight of Kraton 1651 block copolymers in combination with 33        parts by weight of a GE PPO Blendex® HPP821, Witco 40 oil, the        gel heat tested sample retained a deformation of about 33°.    -   13a. Gels of 100 parts by weight of Septon 4055 block copolymers        in combination with 25 parts by weight of a GE PPO Blendex®        HPP821, Witco 40 oil, the gel heat tested sample retained a        deformation of about 30°.    -   14a. Gels of 100 parts by weight of Septon 2006 block copolymers        in combination with 25 parts by weight of a GE PPO Blendex®        HPP821, Witco 40 oil, the gel heat tested sample retained a        deformation of about 15°.    -   15a. Gels of 100 parts by weight of Septon 8006 block copolymers        in combination with 25 parts by weight of a GE PPO Blendex®        HPP821, Witco 40 oil, the gel heat tested sample retained a        deformation of about 35°.    -   16a. Gels of 100 parts by weight of Kraton 1651 block copolymers        in combination with 25 parts by weight of a GE PPO Blendex®        HPP821, Witco 40 oil, the gel heat tested sample retained a        deformation of about 25.    -   17a. Gels of 100 parts by weight of Septon 4055 block copolymers        in combination with 25 parts by weight of Endex 155, Witco 40        oil, the gel heat tested sample retained a deformation of about        75°.    -   18a. Gels of 100 parts by weight of Septon 2006 block copolymers        in combination with 25 parts by weight of Endex 155, Witco 40        oil, the gel heat tested sample retained a deformation of about        55°.    -   19a. Gels of 100 parts by weight of Septon 8006 block copolymers        in combination with 25 parts by weight of Endex 155, Witco 40        oil, the gel heat tested sample retained a deformation of about        30°.    -   20a. Gels of 100 parts by weight of Kraton 1651 block copolymers        in combination with 25 parts by weight of Endex 155, Witco 40        oil, the gel heat tested sample retained a deformation of about        27°.    -   21 a. Gels of 100 parts by weight of Septon 4055 block        copolymers, Blandol, the gel heat tested sample retained a        deformation of about 30°.    -   22a. Gels of 100 parts by weight of Septon 4055 block        copolymers, Carnation, the gel heat tested sample retained a        deformation of about 30°.    -   23a. Gels of 100 parts by weight of Septon 4055 block        copolymers, Klearol, the gel heat tested sample retained a        deformation of about 40°.    -   25a. Gels of 50 parts by weight of Septon 4055 & 50 parts by        weight of Septon 2006 block copolymers, (equal weight of Blandol        and Witco 40 oil), the gel heat tested sample retained a        deformation of about 57°.    -   26a. Gels of 50 parts by weight of Septon 4055 & 50 parts by        weight of Septon 2006 block copolymers, Witco 40 oil, the gel        heat tested sample retained a deformation of about 72′.    -   27a. Gels of 50 parts by weight of Septon 4055 & 50 parts by        weight of Septon 2006 block copolymers, Witco 40 oil, the gel        heat tested sample retained a deformation of about 80°.    -   28a. Gels of 50 parts by weight of Septon 4055 & 50 parts by        weight of Kraton 1651 block copolymers, (equal weight of Blandol        and Witco 40 oil), the gel heat tested sample retained a        deformation of about 55°.    -   29a. Gels of 100 parts by weight of Septon 2006 block        copolymers, (equal weight of Blandol and Witco 40 oil), the gel        heat tested sample retained a deformation of about 45°. The        resulting gel is highly tacky.    -   30a. A Berkeley and V & M PVC fishing baits were 180° U bend        tested @ 50° C. for 1.0 hour, both baits retained a deformation        of about 34°.

When poly(styrene-ethylene-butylene-styrene) (SEBS) is substituted inplace of block copolymer of the invention, the (SEBS) strength isslightly lower, but lack the improved tear resistance and ruptureresistance. For use as fishing bait, (SEBS) gels can also be made softand are also an improvement over conventional plastisol polyvinylchloride fishing baits of corresponding rigidity.

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention, and it is not intended to limit the inventionto the exact details shown above except insofar as they are defined inthe following claims.

1. A gel article in the form of a gel liner comprising a soft gelatinouselastomer composition formed from (I) 100 parts by weight of one or morehydrogenated controlled distribution styrene block copolymer(s) of thegeneral configuration hydrogenated controlled distributionpoly(styrene-isoprene/butadiene-styrene) block copolymer(s) selectedfrom SEB-EB/SEBS, SEBS, SEPS, SEB/SEBS, SEP/SEPS, SEB/SEPS, SEP/SEBS,SEBn, SEPn, and SEEPS, wherein said hydrogenated controlled distributionstyrene block copolymer(s) being a linear, radial, star-shaped, branchedor multiarm copolymer, wherein n is greater than one; from (II) about300 to about 1,600 parts by weight of one or more selectedplasticizer(s) being in sufficient amounts to achieve a gel rigidity offrom about 20 gram Bloom to about 1,800 gram Bloom in combination withor without (III) a selected minor amount of one or more polymers orcopolymers of poly(styrene-butadiene-styrene), poly(styrene-butadiene)n,poly(styrene-isoprene-styrene)n, poly(styrene-isoprene)n,poly(styrene-ethylene-propylene),poly(styrene-ethylene-ethylene-propylene-styrene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)n,poly(styrene-ethylene-butylene)n, polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, orpolyethylene, polyethylene copolymers selected from ultra low densitypoly(ethylene-octene-1 copolymers) and copolymers of ethylene andhexene, poly(ethylene-styrene) interpolymer made by metallocenecatalysts, using single site, constrained geometry additionpolymerization catalysts including terpolymers ofpoly(ethylene/styrene/propylene),poly(ethylene/styrene/4-methyl-1-pentene),poly(ethylene/styrene/hexend-1, ethylene/styrene/octene-1),poly(ethylene/styrene/norbornene), wherein said selected copolymer is alinear, radial, star-shaped, branched multiarm block copolymer or aninterpolymer, wherein n is greater than one; said gel article comprisinga gel with one or multiple rigidity regions, said gel multiple rigidityregions having no physically separable boundaries, or when said gelarticle is formed into a gel composite, wherein said gel being denotedby G, is in contact with a selected material M or in combination withone or more of a different gel, said gel composite is of the combinationGnGn, GnGnGn, GnMn, GnMnGn, MnGnMn, MnGnGn, MnMnMnGnMn, MnGnGnMn,GnMnGnGn, GnGnMnMn, GnGnMnGnGn, GnMnMnGn, GnGnMnGnMnGnGn, GnMnGnMnMn,MnGnMnGnMnGn, GnGnMnMnGn, GnGnMnGnMn, GnGnMnGnMnGn, GnMnGnMnGn, MnMnMnGnor a permutation of one or more of said Gn with Mn; wherein when n is asubscript of M, n is the same or different selected from the groupconsisting of paper, foam, plastic, fabric, metal, metal foil, concrete,wood, glass, glass fibers, ceramics, synthetic resin, synthetic fibersor refractory materials; and wherein when n is a subscript of G, ndenotes a different gel rigidity.
 2. A composite according to claim 1formed into a gel liner for lower limb or above the knee amputeeprosthesis formed by injection molding, extruding, spinning, casting, ordipping of said gel, said (I) block copolymer(s) is selected from one ormore linear, radial, star-shaped, branched or multiarm hydrogenatedcontrolled distributionpoly(styrene-ethylene-butylene-ethylene-butylene/styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene/styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene/styrene-ethylene-propylene-styrene),poly(styrene-ethylene-butylene/styrene-ethylene-propylene-styrene), andpoly(styrene-ethylene-propylene/styrene-ethylene-butylene-styrene).
 3. Aliner according to claim 1 comprising a soft gelatinous elastomercomposition formed from (I) 100 parts by weight of one or more blockcopolymers of hydrogenated controlled distributionpoly(styrene-ethylene-butylene-ethylene-butylene/styrene-ethylene-butylene-styrene),and poly(styrene-ethylene-butylene/styrene-ethylene-butylene-styrene),wherein said hydrogenated controlled distribution styrene blockcopolymer(s) being a linear, radial, star-shaped, branched or multiarmcopolymer, wherein n is greater than one; (II) one or more firstplasticizers with or without one or more second plasticizers being insufficient amounts to achieve a gel rigidity of from about 20 gram Bloomto about 1,800 gram Bloom; said gel formed a gel liner for lower limb orabove the knee amputee prosthesis formed by injection molding,extruding, spinning, casting, or dipping of said gel.
 4. A compositeaccording to claim 1 formed into a gel liner for lower limb or above theknee amputee prosthesis formed by injection molding, extruding,spinning, casting, or dipping of said gel; said liner for: (a.) lowerextremity above the knee prosthesis with socket insert, (b.) lowerextremity, multi-durometer below the knee prosthesis with socket insert,(c.) lower extremity below the knee prosthesis with cuff suspensioninterface, (d.) lower extremity below the knee or above the kneeprosthesis socket insert, suction suspension with locking mechanism,said gel liner for lower limb or above the knee amputee prosthesisformed by injection molding, extruding, spinning, casting, or dipping ofsaid gel.
 5. A gel article according to claim 1 comprising a gel with atleast two different rigidity regions, said gel rigidity regions havingno physically separable boundaries.
 6. A gel article according to claim1 comprising a gel with a first gel rigidity region continuous with asecond gel rigidity region, said first gel rigidity region having a gelrigidity greater than said second gel rigidity region, said first andsecond gel rigidity regions separated by a continuous varying gelrigidity index region having physically inseparable boundaries.